Sulfur Oxidation Ratio Research Articles

Dust event identification and characterization with one-year online observations in Beijing.

Dust storms have a profound impact on air quality, atmospheric chemistry, and human well-being by carrying vast amounts of particles over distances of thousands of kilometers. However, the overall characteristics of these dust events and their influence on secondary pollution in the northern China region are not yet well understood, due to a lack of long-term, comprehensive observations and objective identification techniques. Based on principal component analysis combined with high-time-resolution observations of particulate matter components, here we developed a robust method to identify dust storm events and identified 14 dust events in Beijing in 2019. We further classified these 14 events into two distinct types using Lagrangian particle dispersion models and backward trajectory analysis. The first type (Type I, 9 cases) is characterized by synoptic patterns in Mongolia, originating from the north and directly impacting the Beijing area. The second type (Type II, 5 cases) involves air masses from the north or northwest that temporarily pass through polluted regions south of Beijing before being carried back into the city. Consistently, during Type I dust events, we observed a sharp decrease in secondary inorganic aerosols (SIA) from 65 % to 7 %, as well as in the sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) (from 0.52 to 0.19, and 0.27 to 0.018 respectively). In contrast, during Type II dust events, SIA concentrations increased by 91 %, along with an increase in SOR (1.7 %), NOR (69 %), and f44/f43 (3.0 %), suggesting an enhancement of secondary aerosol formation resulting from the interaction between dust aerosols and gaseous anthropogenic pollutants. Our results demonstrate that dust events and the sub-type of dust events can be identified in an objective manner using the protocol developed in this study and the dynamics should be considered when discussing impacts of dust events on atmospheric chemistry.

Manifesting the hidden pollutants: Quantifying emissions and environmental impact of petroleum refinery on PM2.5

This research thoroughly examined the emissions of primary fine particle and precursors of secondary particles (VOCs, SO2 and NOx) originating from the petroleum refinery operation. The central aim was to quantify the emission factors of fine particulate matter and analyze their spatial dispersion and source contributions, in order to evaluate their environmental impacts.The VOCs emission measurement appeared that the wastewater treatment plant unit was the most significant source of VOCs emissions, with pentane, cyclopentane, and propane being the dominant VOCs species released. The study employed the secondary organic aerosol potential (SOAP), sulfur oxidation ratio (SOR), and nitrogen oxidation ratio (NOR) methodologies to calculate the emissions of secondary PM2.5. The combustion stacks were the principal contributor to secondary PM2.5 emissions, with SO2 being the predominant secondary PM2.5 precursor species contributing to fine particulate matter, accounting for 82.5% of the total secondary PM2.5 emissions. The overall emission factor for the refinery was determined to be 0.31 g secondary PM2.5 per kg of refined crude oil. Furthermore, the analysis indicated that the combustion stacks were the primary contributors to PM2.5 concentrations at all receptor sites, accounting for 64.4%–80.8% of the total contribution, followed by the wastewater treatment unit and storage tanks. The study underscored the importance of focusing on secondary PM2.5 precursor emissions to effectively reduce emissions and environmental concentrations of PM2.5, highlighting the potential for more effective management and mitigation strategies targeting these precursors.

Assessing PM2.5 Dynamics and Source Contributions in Southwestern China: Insights from Winter Haze Analysis

Despite enhancements in pollution control measures in southwestern China, detailed assessments of PM2.5 dynamics following the implementation of the Clean Air Action remain limited. This study explores the PM2.5 concentrations and their chemical compositions during the winter haze period of 2017 across four major urban centers—Chengdu, Chongqing, Guiyang, and Kunming. Significant variability in mean PM2.5 concentrations was observed: Chengdu (71.8 μg m−3) and Chongqing (53.3 μg m−3) recorded the highest levels, substantially exceeding national air quality standards, while Guiyang and Kunming reported lower concentrations, suggestive of comparatively milder pollution. The analysis revealed that sulfate, nitrate, and ammonium (collectively referred to as SNA) constituted a substantial portion of the PM2.5 mass—47.2% in Chengdu, 62.2% in Chongqing, 59.9% in Guiyang, and 32.0% in Kunming—highlighting the critical role of secondary aerosol formation. The ratio of NO3−/SO42− and nitrogen oxidation ratio to sulfur oxidation ratio (NOR/SOR) indicate a significant transformation of NO2 under conditions of heavy pollution, with nitrate formation playing an increasingly central role in the haze dynamics, particularly in Chengdu and Chongqing. Utilizing PMF for source apportionment, in Chengdu, vehicle emissions were the predominant contributor, accounting for 33.1%. Chongqing showed a similar profile, with secondary aerosols constituting 36%, followed closely by vehicle emissions. In contrast, Guiyang’s PM2.5 burden was heavily influenced by coal combustion, which contributed 46.3%, reflecting the city’s strong industrial base. Kunming presented a more balanced source distribution. Back trajectory analysis further confirmed the regional transport of pollutants, illustrating the complex interplay between local and distant sources. These insights underscore the need for tailored, region-specific air quality management strategies in southwestern China, thereby enhancing our understanding of the multifaceted sources and dynamics of PM2.5 pollution amidst ongoing urban and industrial development.

Multi-scale analysis of the chemical and physical pollution evolution process from pre-co-pollution day to PM2.5 and O3 co-pollution day

PM2.5 and O3 are two of the main air pollutants that have adverse impacts on climate and human health. The evolution process of PM2.5 and O3 co-pollution are of concern because of the increased frequency of PM2.5 and O3 co-pollution days. Here, we examined the chemical coupling and revealed the driving factors of the PM2.5 and O3 co-pollution evolution process from cleaning day, PM2.5 pollution day, or O3 pollution day, applied by theoretical analysis and model calculation methods. The results demonstrate that PM2.5 and O3 co-pollution day frequently occurred with high concentrations of gaseous precursors and higher sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR), which we attribute to the enhancement of atmospheric oxidation capacity (AOC). The AOC is positively correlated with O3 and weakly correlated with PM2.5. In addition, we found that the correlation coefficients of PM2.5-NO2 (0.62) were higher than that of PM2.5-SO2 (0.32), highlighting the priority of NOx controlling to mitigate PM2.5 pollution. Overall, our discovery can provide scientific evidence to design feasible solutions for the controlling PM2.5 and O3 co-pollution process.

Chemical characterization and source apportionment of PM2.5 in a Northeastern China city during the epidemic period.

To investigate the influence of COVID-19 lockdown measures on PM2.5 and its chemical components in Shenyang, PM2.5 samples were continuously collected from January 1 to May 31, 2020. The samples were then analyzed for water-soluble inorganic ions, metal elements, organic carbon, and elemental carbon. The findings indicated a significant decrease in PM2.5 and its various chemical components during the lockdown period, compared to pre-lockdown levels (p < 0.05), suggesting a substantial improvement in air quality. Water-soluble inorganic ions (WSIIs) were identified as the primary contributors to PM2.5, accounting for 47% before the lockdown, 46% during the lockdown, and 37% after the lockdown. Ionic balance analysis revealed that PM2.5 exhibited neutral, weakly alkaline, and alkaline characteristics before, during, and after the lockdown, respectively. NH4+ was identified as the main balancing cation and was predominantly present in the form of NH4NO3 in the absence of complete neutralization of SO42- and NO3-. Moreover, the higher sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR), along with the significant increase in PM2.5/EC, suggested intense secondary transformation during the lockdown period. The elevated OC/EC ratio during the lockdown period implied higher secondary organic carbon (SOC), and the notable increase in SOC/EC ratio indicated a significant secondary transformation of total carbon. The enrichment factor (EF) results revealed that during the lockdown, 9 metal elements (As, Sn, Pb, Zn, Cu, Sb, Ag, Cd, and Se) were substantially impacted by anthropogenic emissions. Source analysis of PMF was employed to identify the sources of PM2.5 in Shenyang during the study period, and the analysis identified six factors: secondary sulfate and vehicle emissions, catering fume sources, secondary nitrate and coal combustion emissions, dust sources, biomass combustion, and industrial emissions, with secondary sulfate and vehicle emissionsand catering fume sourcescontributing the most to PM2.5.

Pollution characteristics and transformation mechanisms of secondary inorganic components during winter heavy pollution in Handan city in 2018–2020

The mechanism of secondary transformation of nitrate and sulfate under different relative humidity (RH), and different atmospheric oxidizing conditions is still controversial. This study focuses on the winter heavy pollution process in Handan city from 2018 to 2020, and the following results were obtained: The average concentration of PM2.5 showed a decreasing trend from year to year, but the SNA (SO42−, NO3− and NH4+) showed an increasing trend from year to year, and the concentration of nitrate exceeded that of sulfate. During the haze formation period from 2018 to 2020, a significant disparity was observed in NO2 and SO2 emissions, with NO2 emissions surpassing those of SO2. Mobile sources were found to contribute more emissions than fixed sources, particularly during the haze persistence period (HP). However, sulfate conversion outweighed nitrate conversion. HighRH and photochemical reactions induced by ozone favored the formation of nitrate and sulfate, which formated heavy haze. When 40% ≤ RH ≤ 70%, atmospheric oxidants (Ox = O3 + NO2) concentration was the highest, nitrogen oxidation ratio (NOR) and sulfur oxidation ratio (SOR) increased rapidly, and nitrate was mainly generated by photochemical reactions during daytime. When RH > 70% and the concentration of Ox was low, RH will weaken the photochemical intensity. Therefore, the liquid-phase oxidation reaction of N2O5 contributed significantly to atmospheric nitrate at night, and the liquid-phase oxidation reaction of sulfate was faster than the gas-phase one. Local emissions contributed significantly to particulate matter pollution during heavy pollution in 2018–2020, and the main sources were secondary conversion, coal combustion, biomass burning, and road dust.

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.

Atmospheric environment characteristic of severe dust storms and its impact on sulfate formation in downstream city

This study comprehensively investigated the impact of dust storms (DSs) on downstream cities, by selecting representative DS events. In this paper, we discussed the characteristics of meteorological conditions, air pollutants, PM2.5 components, and their influence on sulfate formation mechanisms. During DSs, strong winds, reaching speeds of up to 10 m/s, led to significant increases in PM10 and PM2.5, with maximum concentrations of 2684.5 and 429 μg/m3, respectively. Primary gaseous pollutants experienced substantial reductions, with decline rates of 48.1, 34.9, 36.8, and 9.0 % for SO2, NO2, NH3, and CO, respectively. Despite a notable increase in PM2.5 concentrations, only 7.6 % of the total mass of PM2.5 was attributed to ionic and carbonaceous components, a much lower value than observed before the DSs (77.3 %). Concentrations of Fe, Ti, and Mn exhibited increases by factors of 6.5–14.1, 10.4–17.0, and 1.6–4.7, respectively. In contrast to the significant decrease of >76.2 % in nitrogen oxidation ratio (NOR), sulfur oxidation ratio (SOR) remained at a relatively high level, displaying a strong positive correlation with high concentrations of Fe, Mn, and Ti. Quantitative analysis revealed an average increase of 0.187 and 0.045 μg/m3 in sulfate from natural sources and heterogeneous generation, respectively. The heterogeneous reaction on mineral dust was closely linked to atmospheric humidity, radiation intensity, the form of metal existence, and concentrations of it. High concentrations of titanium dioxide and iron‑manganese oxides in mineral dust promoted heterogeneous oxidation of SO2 through photocatalysis during the daytime and metal ion catalysis during the nighttime. This study establishes that the metal components in mineral dust promote heterogeneous sulfate formation, quantifies the yield of sulfate generated as a result, and provides possible mechanisms for heterogeneous sulfate formation.

Important Role of Low Cloud and Fog in Sulfate Aerosol Formation During Winter Haze Over the North China Plain

AbstractSulfate aerosol greatly contributes to wintertime haze pollution in emission‐intensive regions like the North China Plain (NCP) in China. Fast sulfate increase and accumulation are usually recorded during winter haze; however, the multiphase oxidation of sulfur dioxide (SO2) and the physical processes affecting near‐surface sulfate are not fully understood. By combining in situ observations and numerical simulations, we found that high sulfur oxidation ratios (&gt;0.6) under heavily polluted conditions are associated with low clouds and fog over NCP, induced by the moist southerly airflow. Thick low clouds and high SO2 levels in NCP provide a reaction environment for sulfate production. The sulfate production rate in cloud water can reach 0.5–1.3 μg m−3 h−1. The results demonstrate that the vertical mixing of sulfate generated within the cloud water to the surface plays a significant role in rapid sulfate production, highlighting the importance of understanding cloud‐water processes in haze pollution.

Influence of atmospheric oxidation capacity on atmospheric particulate matters concentration in Lanzhou

The atmospheric oxidation capacity (AOC) reflects the removal rate of atmospheric pollutants, and this index is typically characterized by the oxidant concentration or total reaction rate. The AOC plays a crucial role in the formation of atmospheric particulate matters and serves as an important indicator for studying changes in the concentration. In this study, we analyse the characteristics of atmospheric oxidants in Lanzhou based on data in the year of 2020 and 2021 retrieved from the Atmospheric Comprehensive Observation Station in Lanzhou. Empirical equations are applied to estimate the impact of atmospheric oxidative properties secondary generation concentrations of atmospheric particulate matters with different particle sizes. The results indicate that the annual average values of Ox were 146 μg/m3 in 2020 and 139 μg/m3 in 2021. The AOC was the highest in summer and lowest in winter. The correlation coefficient between O3 and Ox was significantly higher than that between NO2 and Ox, suggesting that O3 exerted a greater impact on the AOC in Lanzhou. A low AOC (MDA8 O3 ≤ 100 μg/m3) promoted the oxidation process of VOCs and other precursors, leading to the generation of secondary aerosols and subsequent formation of secondary particles. There were negative correlations between Ox and atmospheric particulate matters, secondary inorganic components, sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR), indicating that excessively high levels of Ox could inhibit the conversion rate of SO2 and NO2 into their respective forms to a certain extent.

Aerosol acidity and its impact on sulfate and nitrate of PM2.5 in southern city of Beijing-Tianjin-Hebei region

Aerosol acidity, similar to the pH of a solution, influences the water-phase reactions within aerosols, thereby impacting the formation and composition of particle components. This study investigated the chemical composition of PM2.5, pH of PM2.5 and its impact on formation of SO42− and NO3− in Handan city from March 2015 to February 2016. The results showed that NO3− was the dominant inorganic secondary ion in PM2.5, accounting for 16.4% of PM2.5, slightly higher than SO42− at 14.2%. The average pH of PM2.5 in Handan was 4.3, indicating moderate acidity, with higher acidity observed in spring and winter. Nitrogen oxidation ratio (NOR) was synergistically influenced by pH and aerosol water content (AWC), while sulfur oxidation ratio (SOR) was associated with high aerosol acidity or AWC. The activity coefficient of NO3− exhibited a negative correlation with activity coefficient of [H+], with an R2 value of −0.20 (“-” means negative correlation). Conversely, a positive correlation was observed between activity coefficient of SO42− and [H+], with an R2 value of 0.19. The partition coefficient (ε(NO3−)) of nitrate, representing its assignment to the solid phase, is given by the function y = −0.5x2+4.2x-7.6 (R2 = 0.60), where x corresponds to pH and y corresponds to ε(NO3−). It suggested that NO3− is most likely to enter the solid phase in significant quantities under moderately acidity condition (at around pH = 4.2). A significant correlation observed between pH, surface tension, and particle radius, indicating that pH influences the aging process of aerosols. However, the impact of pH varies depending on the pollution episode.

Characterization, Sources, and Chemical Processes of Submicron Aerosols at a Mountain Site in Central China

AbstractA field campaign (29 May to 14 June 2018) was conducted at a mountain site in central China. The chemical composition of non‐refractory submicron particulate matter (NR‐PM1) and the particle number size distribution (PNSD) were measured, respectively. The mean NR‐PM1 mass concentration was 20.94 ± 10.14 μg m−3, among which organics (47%) was the most abundant component, followed by sulfate (37%), ammonium (11%), nitrate (4%), and chloride (1%). Notably, sulfate accounted for more than 70% of the secondary inorganic aerosols. Positive matrix factorization (PMF) analysis of the composition data resulted in three organic aerosol (OA) factors: hydrocarbon‐like OA (HOA), oxygenated OA I (OOA‐I), and oxygenated OA II (OOA‐II). The secondary organic aerosol (SOA) composed of the latter two factors (SOA: OOA‐I + OOA‐II) was dominant in OA (80.7%). The PMF analysis of the PNSD data yielded three factors: new particle formation related mode, growth mode, and accumulation mode, among which the last factor dominated both number and volume ratios. The sulfate formation was characterized by the sulfur oxidation ratio (SOR), heterogeneous sulfate production rate (Phet), and gaseous sulfuric acid concentration, representing secondary sulfate transformation, heterogeneous reactions, and gas phase reactions, respectively. The results showed that Phet was well correlated with both sulfate concentrations and SOR, especially during the polluted periods. Our study demonstrates that photochemically‐driven heterogeneous reactions contribute dominantly to the sulfate formation and SOA is formed predominantly by photochemical oxidation of volatile organic compounds under high temperatures and ultraviolet (UV) intensities, and NOX concentrations on Mt. Wudang during the campaign period.

Atmospheric Oxidation Capacity and Its Impact on the Secondary Inorganic Components of PM2.5 in Recent Years in Beijing: Enlightenment for PM2.5 Pollution Control in the Future

In recent years, the concentrations of PM2.5 in urban ambient air in China have been declining; however, the strong atmospheric oxidation capacity (AOC) represents challenges to the further reduction of PM2.5 concentration and the continuous improvement of ambient air quality in China in the future, since the overall AOC is still at a high level. For this paper, based on ground observation data recorded in Beijing from 2016 to 2019, the variation in AOC was characterized according to the concentration of odd oxygen (OX = O3 + NO2). The concentrations of the primary and secondary components of PM2.5 were analyzed using empirical formulas, the correlation between AOC and the concentrations of secondary PM2.5 and the secondary inorganic components (SO42−, NO3−, NH4+, and SNA) in Beijing were explored, the impact of atmospheric photochemical reaction activity on the generation of atmospheric secondary particles was evaluated, and the impact of atmospheric oxidation variations on PM2.5 concentrations and SNA in Beijing was investigated. The results revealed that OX concentrations reached their peak in 2016 and reached their lowest point in 2019. The OX concentrations followed a descending seasonal trend of summer, spring, autumn, and winter, along with a spatial descending trend from urban observation stations to suburban stations and background stations. The degree of photochemical activity and the magnitude of the AOC have a large influence on the production of atmospheric secondary particles. When the photochemical reaction was more active and the AOC was stronger, the mass concentrations of the secondary generated PM2.5 fraction were higher and accounted for a higher proportion of the total PM2.5 mass concentrations. In the PM2.5 fraction, SNA accounted for 50.7% to 94.4% of the total mass concentrations of water-soluble inorganic ions in the field observations. Higher concentrations of the atmospheric oxidant OX in ambient air corresponded to a higher sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR), suggesting that the increase in AOC could promote the increase of PM2.5 concentration. Based on a relationship analysis of SOR, NOR, and OX, it was inferred that the relationship between OX and SOR and the relationship between OX and NOR were both nonlinear. Therefore, when establishing PM2.5 control strategies in Beijing in the future, the impact of the AOC on PM2.5 generation should be fully considered, and favorable measures should be taken to properly regulate the AOC, which would be more effective when carrying out further control measures regarding PM2.5 pollution.

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.

Characterisation and Source Identification of Inorganic Water-Soluble Ions in PM2.5 in a Small-Size Steel City of China

Ambient PM2.5 samples were collected in Laiwu, a small industrial city in China known for steel production, to measure and evaluate the mass concentrations of PM2.5 and the inorganic water-soluble ions (IWS ions). The highest PM2.5 value recorded was 251.28 μg/m3, which occurred during winter and was lower than other major Chinese cities. The spatial distribution showed that the center of the city, which is connected to the downtown area, was heavily polluted (170 μg/m3 higher) compared to the suburbs. With the exception of winter, the weight of PM2.5 was dominated by IWS ions, with three secondary ions (NO3 -, SO4 2-, and NH4 +) accounting for more than 70% of the total ions in mass. This percentage is higher than that of big cities. An increase in sulfur oxidation ratios (SOR), nitrogen oxidation rate (NOR), and anion equivalent/cation equivalent (AE/CE) indicated that the atmosphere in Laiwu was more oxidized than other big cities. The ion analysis revealed that PM2.5 was highly correlated with NO3 -, SO4 2-, and NH4 +. The principal component analysis indicated that district heating during winter and industrial output and secondary transformation during summer were the major sources of the water-soluble ions. The backward trajectory study identified the north of Shandong Province as the likely source-area that affected air quality in Laiwu.

Insight into the non-linear responses of particulate sulfate to reduced SO2 concentration: A perspective from the aqueous-phase reactions in a megacity in Northern China

The non-linear relationship between particle sulfate and SO2 is still unclear. Continuous observations were conducted in a typical city in Northern China from 2017 to 2020. SO2 concentration continually decreased, however, the SO42− concentration and the sulfur oxidation ratio increased in 2018–2019. The major reason might be the variations of sulfate formation by the aqueous-phase reactions, especially for the O2 + TMI oxidation (oxygen catalyzed by transition-metal ions). Particle pH, SO2, and Mn concentration were the main factors affecting the O2 + TMI reaction rate. Sensitivity analysis indicated that the decrease of the O2 + TMI reaction rate caused by SO2 or Mn concentration dropping by half can only offset the increased rate caused by a 0.1 unit decrease in particle pH. Considering the actual atmospheric environment in Northern China, if the particle pH continues to drop, the slow decline of SO2 and Mn concentration may not prevent the increase in the O2 + TMI oxidation rate. In addition to meteorological parameters, the concentrations of SO42−, crustal elements, and total ammonium were the primary factors for the decrease in particle pH in the past 3 years. Therefore, the impact of pH on sulfate formation must be considered when controlling dust and ammonia emissions.

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.

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) &lt; 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 &lt; 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) &lt; 0.3, sulfur oxidation ratio (SOR) &lt; 0.4, ammonia transition ratio (NTR) &lt; 0.7 and the moral ratio of NO3-/SO42-=2:1. When ALWC &gt; 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 (&gt;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.

Pollution Characteristics and Sources of Water-soluble Ions in PM2.5 in Zhengzhou City

In order to explore the pollution characteristics, seasonal variations, and sources of water-soluble inorganic ions (WSIIs) in PM2.5 in Zhengzhou, PM2.5 samples were seasonally collected from December 2020 to October 2021; then, combining gaseous pollutants (SO2, NO2, and O3) and meteorological parameters (temperature and relative humidity), nine WSIIs (NO3-, NH4+, SO42-, Ca2+, K+, Na+, Mg2+, F-, and Cl-) were analyzed. The results showed that the annual average concentration of the total water-soluble ions (TWSIIs) was (39.34±21.56) μg·m-3for the four seasons, showing obvious seasonal variations with the maximum value in winter and the minimum value in summer. Annual PM2.5 was slightly alkaline in Zhengzhou, and NH4+ most likely existed in the form of NH4NO3 and (NH4)2SO4. The average sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were 0.35 and 0.19, respectively, indicating that SO42- and NO3- mainly derived from secondary formation. The main potential source regions of WSIIs obtained by the concentration weight trajectory (CWT) model showed temporal and spatial variations. The significant sources of WSIIs based on principal component analysis (PCA) were dust, secondary generation, combustion, and industrial activities, which were obviously influenced by wind direction and speed in Zhengzhou.

Characteristics of PM2.5 and secondary inorganic pollution formation during the heating season of 2021 in Beijing

Water-soluble inorganic ions (WSIIs) were measured online in Beijing during the heating season of 2021, during which Beijing 2022 Olympic and Paralympic Winter Games were hosted. The characteristics of PM2.5 and water-soluble inorganic ions were investigated in general, as well as during the clean period, polluted period, and Olympic and Paralympic Winter Games periods. It was found that most of the polluted episodes occurred under conditions of low wind speed, temperature inversion, and high relative humidity. The total mass concentration of water-soluble inorganic ions during the polluted period and the clean period accounted for 38.2% and 61.4% of the PM2.5 mass concentration, respectively. Both the sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) showed a strong relationship with relative humidity. During the polluted period, the concentrations of secondary aerosols such as sulfate, nitrate, and ammonium (SNA) increased significantly. Secondary transformation was enhanced compared with that in the clean period. A polluted process after a snowfall event was selected to explore the mechanism of sulfate and nitrate formation under high relative humidity. The results would be beneficial to understanding the causes of pollution and helping the government to formulate effective measures to control air pollution in winter.