Recent Progress in Atmospheric Chemistry Research in China: Establishing a Theoretical Framework for the "Air Pollution Complex".

Atmospheric chemistry research has been growing rapidly in China in the last 25 years since the concept of the "air pollution complex" was first proposed by Professor Xiaoyan TANG in 1997. For papers published in 2021 on air pollution (only papers included in the Web of Science Core Collection database were considered), more than 24 000 papers were authored or co-authored by scientists working in China. In this paper, we review a limited number of representative and significant studies on atmospheric chemistry in China in the last few years, including studies on (1) sources and emission inventories, (2) atmospheric chemical processes, (3) interactions of air pollution with meteorology, weather and climate, (4) interactions between the biosphere and atmosphere, and (5) data assimilation. The intention was not to provide a complete review of all progress made in the last few years, but rather to serve as a starting point for learning more about atmospheric chemistry research in China. The advances reviewed in this paper have enabled a theoretical framework for the air pollution complex to be established, provided robust scientific support to highly successful air pollution control policies in China, and created great opportunities in education, training, and career development for many graduate students and young scientists. This paper further highlights that developing and low-income countries that are heavily affected by air pollution can benefit from these research advances, whilst at the same time acknowledging that many challenges and opportunities still remain in atmospheric chemistry research in China, to hopefully be addressed over the next few decades.

Effects of heterogeneous reaction with NO2 on ice nucleation activities of feldspar and Arizona Test Dust.

Mineral dust is an important type of ice nucleating particles in the troposphere; however, the effects of heterogeneous reactions on ice nucleation (IN) activities of mineral dust remain to be elucidated. A droplet-freezing apparatus (Guangzhou Institute of Geochemistry Ice Nucleation Apparatus, GIGINA) was developed in this work to measure IN activities of atmospheric particles in the immersion freezing mode, and its performance was validated by a series of experimental characterizations. This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust (ATD) particles before and after heterogeneous reaction with NO2 (10±0.5 ppmv) at 40% relative humidity. The surface coverage of nitrate, θ(NO3-), increased to 3.1±0.2 for feldspar after reaction with NO2 for 6 hr, and meanwhile the active site density per unit surface area (ns) at -20°C was reduced from 92±5 to <1.0 cm-2 by about two orders of magnitude; however, no changes in nitrate content or IN activities were observed for further increase in reaction time (up to 24 hr). Both nitrate content and IN activities changed continuously with reaction time (up to 24 hr) for ATD particles; after reaction with NO2 for 24 hr, θ(NO3-) increased to 1.4±0.1 and ns at -20°C was reduced from 20±4 to 9.7±1.9 cm-2 by a factor of ∼2. Our work suggests that heterogeneous reaction with NO2, an abundant reactive nitrogen species in the troposphere, may significantly reduce IN activities of mineral dust in the immersion freezing mode.

Heterogeneous reaction of NO2 with feldspar, three clay minerals and Arizona Test Dust.

Heterogeneous reaction of NO2 with mineral dust aerosol may play important roles in troposphere chemistry, and has been investigated by a number of laboratory studies. However, the influence of mineralogy on this reaction has not been well understood, and its impact on aerosol hygroscopicity is not yet clear. This work investigated heterogeneous reactions of NO2 (∼10 ppmv) with K-feldspar, illite, kaolinite, montmorillonite and Arizona Test Dust (ATD) at room temperature as a function of relative humidity (<1% to 80%) and reaction time (up to 24 hr). Heterogeneous reactivity towards NO2 was low for illite, kaolinite, montmorillonite and ATD, and uptake coefficients of NO2, γ(NO2), were determined to be around or smaller than 1×10-8; K-feldspar exhibited higher reactivity towards NO2, and CaCO3 is most reactive among the nine mineral dust samples considered in this and previous work. After heterogeneous reaction with NO2 for 24 hr, increase in hygroscopicity was nearly insignificant for illite, kaolinite and montmorillonite, and small but significant for K-feldspar; in addition, large increase in hygroscopicity was observed for ATD, although the increase in hygroscopicity was still smaller than CaCO3.

Hygroscopic properties of sodium and potassium salts as related to saline mineral dusts and sea salt aerosols.

Mineral dust, soil, and sea salt aerosols are among the most abundant primary inorganic aerosols in the atmosphere, and their hygroscopicity affects the hydrological cycle and global climate. We investigated the hygroscopic behaviors of six Na- and K-containing salts commonly found in those primary organic aerosols. Their hygroscopic growths as a function of relative humidity (RH) agree well with thermodynamic model prediction. Temperature dependence of deliquescence RH (DRH) values for five of those salts was also investigated, which are comparable to those in literature within 1%-2% RH, most showing negative dependence on temperature. Hygroscopic growth curves of real-world soil and sea salt samples were also measured. The hygroscopic growths of two more-hydroscopic saline soil samples and of sea salt can be predicted by the thermodynamic model based on the measured water-soluble ionic composition. The substantial amounts of water-soluble ions, including Na+ and K+, in saline soil samples imply that even nascent saline soil samples are quite hygroscopic at high-RH (>80%) conditions. For three less-hygroscopic dust samples, however, measurements showed higher water uptake ability than that predicted by the thermodynamic model. The small amount of water taken up by less-hygroscopic dust samples suggests that dust particles might contain thin layers of water even to very low RH. The results of this study provide a comprehensive characterization of the hygroscopicity of Na- and K-containing salts as related to their roles in the hygroscopic behaviors of saline mineral dusts and sea salt aerosols.

Aerosol Phase State and Its Link to Chemical Composition and Liquid Water Content in a Subtropical Coastal Megacity.

Particle phase state plays a key role in gas-particle partitioning, heterogeneous and multiphase reactions, and secondary aerosol formation. In this work, the rebound fraction and chemical composition of submicron particles were simultaneously measured to investigate the particle phase state and its link to chemical composition in a subtropical coastal urban city (Shenzhen, China). Submicron particles were found to be in the liquid state for most of the measurement period in spring. During the sampling time, both high relative humidity (RH, ranged from 40% to 93%) and inorganic mass fraction in particles (62.6 ± 12.4% of dry particles, on average) resulted in abundant aerosol liquid water (43 ± 6% in the wet PM1, on average), which may liquefy the particles. Considering the high frequency of ambient RH > 60% and large inorganic mass fraction in aerosol particles, we deduced that particles were in the liquid state throughout the year in coastal urban areas, where this study was performed. The liquid phase particles may accelerate the mass transfer of reactive trace gases and multiphase reactions, thereby enhanced secondary aerosol formation, further resulting in a rapid growth in aerosol mass. Our work suggested that in regions heavily impacted by SO2 and NO x emissions, especially in developing countries, the presence of inorganics could significantly impact the phase state of ambient aerosol particles, and thus the mixing state of inorganic and organic matter should be taken into account for the investigation of the aerosol phase state in urban environments.

Oxalate Formation Enhanced by Fe-Containing Particles and Environmental Implications.

We used a single particle mass spectrometry to online detect chemical compositions of individual particles over four seasons in Guangzhou. Number fractions (Nfs) of all the measured particles that contained oxalate were 1.9%, 5.2%, 25.1%, and 15.5%, whereas the Nfs of Fe-containing particles that were internally mixed with oxalate were 8.7%, 23.1%, 45.2%, and 31.2% from spring to winter, respectively. The results provided the first direct field measurements for the enhanced formation of oxalate associated with Fe-containing particles. Other oxidized organic compounds including formate, acetate, methylglyoxal, glyoxylate, purivate, malonate, and succinate were also detected in the Fe-containing particles. It is likely that reactive oxidant species (ROS) via Fenton reactions enhanced the formation of these organic compounds and their oxidation product oxalate. Gas-particle partitioning of oxalic acid followed by coordination with Fe might also partly contribute to the enhanced oxalate. Aerosol water content likely played an important role in the enhanced oxalate formation when the relative humidity is >60%. Interactions with Fe drove the diurnal variation of oxalate in the Fe-containing particles. The study could provide a reference for model simulation to improve understanding on the formation and fate of oxalate, and the evolution and climate impacts of particulate Fe.

Interactions of Water with Mineral Dust Aerosol: Water Adsorption, Hygroscopicity, Cloud Condensation, and Ice Nucleation.

Mineral dust aerosol is one of the major types of aerosol present in the troposphere. The molecular level interactions of water vapor with mineral dust are of global significance. Hygroscopicity, light scattering and absorption, heterogneous reactivity and the ability to form clouds are all related to water-dust interactions. In this review article, experimental techniques to probe water interactions with dust and theoretical frameworks to understand these interactions are discussed. A comprehensive overview of laboratory studies of water adsorption, hygroscopicity, cloud condensation, and ice nucleation of fresh and atmspherically aged mineral dust particles is provided. Finally, we relate laboratory studies and theoretical simulations that provide fundemental insights into these processes on the molecular level with field measurements that illustrate the atmospheric significance of these processes. Overall, the details of water interactions with mineral dust are covered from multiple perspectives in this review article.

Competition between Displacement and Dissociation of a Strong Acid Compared to a Weak Acid Adsorbed on Silica Particle Surfaces: The Role of Adsorbed Water.

The adsorption of nitric (HNO3) and formic (HCOOH) acids on silica particle surfaces and the effect of adsorbed water have been investigated at 296 K using transmission FTIR spectroscopy. Under dry conditions, both nitric and formic acids adsorb reversibly on silica. Additionally, the FTIR spectra show that both of these molecules remain in the protonated form. At elevated relative humidities (RH), adsorbed water competes both for surface adsorption sites with these acids as well as promotes their dissociation to hydronium ions and the corresponding anions. Compared to HNO3, the extent of dissociation is much smaller for HCOOH, very likely because it is a weaker acid. This study provides valuable insights into the interaction of HNO3 and HCOOH with silica surface on the molecular level and further reveals the complex roles of surface-adsorbed water in atmospheric heterogeneous chemistry of mineral dust particles-many of these containing silica.

Heterogeneous Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

We have investigated the heterogeneous uptake of gaseous acetic acid on different oxides including γ-Al2O3, SiO2, and CaO under a range of relative humidity conditions. Under dry conditions, the uptake of acetic acid leads to the formation of both acetate and molecularly adsorbed acetic acid on γ-Al2O3 and CaO and only molecularly adsorbed acetic acid on SiO2. More importantly, under the conditions of this study, dimers are the major form for molecularly adsorbed acetic acid on all three particle surfaces investigated, even at low acetic acid pressures under which monomers are the dominant species in the gas phase. We have also determined saturation surface coverages for acetic acid adsorption on these three oxides under dry conditions as well as Langmuir adsorption constants in some cases. Kinetic analysis shows that the reaction rate of acetic acid increases by a factor of 3-5 for γ-Al2O3 when relative humidity increases from 0% to 15%, whereas for SiO2 particles, acetic acid and water are found to compete for surface adsorption sites.

Optical and Physicochemical Properties of Brown Carbon Aerosol: Light Scattering, FTIR Extinction Spectroscopy, and Hygroscopic Growth.

A great deal of attention has been paid to brown carbon aerosol in the troposphere because it can both scatter and absorb solar radiation, thus affecting the Earth's climate. However, knowledge of the optical and chemical properties of brown carbon aerosol is still limited. In this study, we have investigated different aspects of the optical properties of brown carbon aerosol that have not been previously explored. These properties include extinction spectroscopy in the mid-infrared region and light scattering at two different visible wavelengths, 532 and 402 nm. A proxy for atmospheric brown carbon aerosol was formed from the aqueous reaction of ammonium sulfate with methylglyoxal. The different optical properties were measured as a function of reaction time for a period of up to 19 days. UV/vis absorption experiments of bulk solutions showed that the optical absorption of aqueous brown carbon solution significantly increases as a function of reaction time in the spectral range from 200 to 700 nm. The analysis of the light scattering data, however, showed no significant differences between ammonium sulfate and brown carbon aerosol particles in the measured scattering phase functions, linear polarization profiles, or the derived real parts of the refractive indices at either 532 or 402 nm, even for the longest reaction times with greatest visible extinction. The light scattering experiments are relatively insensitive to the imaginary part of the refractive index, and it was only possible to place an upper limit of k ≤ 0.01 on the imaginary index values. These results suggest that after the reaction with methylglyoxal the single scattering albedo of ammonium sulfate aerosol is significantly reduced but that the light scattering properties including the scattering asymmetry parameter, which is a measure of the relative amount of forward-to-backward scattering, remain essentially unchanged from that of unprocessed ammonium sulfate. The optical extinction properties in the mid-IR range (800 to 7000 cm(-1)) also showed no significant changes in either the real or the imaginary parts of the refractive indices for brown carbon aerosol particles when compared to ammonium sulfate. Therefore, changes in the optical properties of ammonium sulfate in the mid-IR spectral range due to reaction with methylglyoxal appear to be insignificant. In addition to these measurements, we have characterized additional physicochemical properties of the brown carbon aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to ammonium sulfate, brown carbon aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidities. Overall, our study provides new details of the optical and physicochemical properties of a class of secondary organic aerosol which may have important implications for atmospheric chemistry and climate.

Formation of nitrogen-containing gas phase products from the heterogeneous (photo)reaction of NO2 with gallic acid.

Heterogeneous reaction of gas phase NO2 with atmospheric humic-like substances (HULIS) is potentially an important source of volatile organic compounds (VOCs) including nitrogen (N)-containing compounds, a class of brown carbon of emerging importance. However, the role of ubiquitous water-soluble aerosol components in this multiphase chemistry, namely nitrate and iron ions, remains largely unexplored. Here, we used secondary electrospray ionization ultrahigh-resolution mass spectrometry for real-time measurements of VOCs formed during the heterogeneous reaction of gas phase NO2 with a solution containing gallic acid (GA) as a proxy of HULIS at pH 5 relevant for moderately acidic aerosol particles. Results showed that the number of detected N-containing organic compounds largely increased from 4 during the NO2 reaction with GA in the absence of nitrate and iron ions to 55 in the presence of nitrate and iron ions. The N-containing compounds have reduced nitrogen functional groups, namely amines, imines and imides. These results suggest that the number of N-containing compounds is significantly higher in deliquescent aerosol particles due to the influence of relatively higher ionic strength from nitrate ions and complexation/redox reactivity of iron cations compared to that in the dilute aqueous phase representative of cloud, fog, and rain water.

A database for deliquescence and efflorescence relative humidities of compounds with atmospheric relevance.

Deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH), the two parameters that regulate phase state and hygroscopicity of substances, play important roles in atmospheric science and many other fields. A large number of experimental studies have measured the DRH and ERH values of compounds with atmospheric relevance, but these values have not yet been summarized in a comprehensive manner. In this work, we develop for the first-of-its-kind a comprehensive database which compiles the DRH and ERH values of 110 compounds (68 inorganics and 42 organics) measured in previous studies, provide the preferred DRH and ERH values at 298 K for these compounds, and discuss the effects of a few key factors (e.g., temperature and particle size) on the measured DRH and ERH values. In addition, we outline future work that will broaden the scope of this database and enhance its accessibility.

Mass fractions, solubility, speciation and isotopic compositions of iron in coal and municipal waste fly ash.

Deposition of anthropogenic aerosols may contribute significantly to dissolved Fe in the open ocean, affecting marine primary production and biogeochemical cycles; however, fractional solubility of Fe is not well understood for anthropogenic aerosols. This work investigated mass fractions, solubility, speciation and isotopic compositions of Fe in coal and municipal waste fly ash. Compared to desert dust (3.1 ± 1.1%), the average mass fraction of Fe was higher in coal fly ash (6.2 ± 2.7%) and lower in municipal waste fly ash (2.6 ± 0.4%), and the average Fe/Al ratios were rather similar for the three types of particles. Municipal waste fly ash showed highest Fe solubility (1.98 ± 0.43%) in acetate buffer (pH: 4.3), followed by desert dust (0.43 ± 0.30%) and coal fly ash (0.24 ± 0.28%), suggesting that not all the anthropogenic aerosols showed higher Fe solubility than desert dust. For the samples examined in our work, amorphous Fe appeared to be an important controlling factor for Fe solubility, which was not correlated with particle size or BET surface area. Compared to desert dust (-0.05‰ to 0.21‰), coal and municipal waste fly ash showed similar or even higher δ56Fe values for total Fe (range: 0.05‰ to 0.75‰), implying that the presence of coal or municipal waste fly ash may not be able to explain significantly smaller δ56Fe values reported for total Fe in ambient aerosols affected by anthropogenic sources.

Hygroscopicity and cloud condensation nucleation activities of hydroxyalkylsulfonates.

Hydroxyalkylsulfonates may contribute significantly to atmospheric particles; however, their hygroscopic properties and cloud condensation nuclei (CCN) activities remain unknown. In this study, three complementary techniques were utilized to examine the hygroscopicity of sodium hydroxymethanesulfonate (NaHMS), sodium 2-hydroxyethylsulfonate (NaHES), and ammonium 2-hydroxyethylsulfonate (NH4HES) under subsaturated and supersaturated environments. The mass changes in the three hydroxyalkylsulfonates at different relative humidities at 25 °C were examined by a vapor sorption analyzer, and the mass growth factors were measured to be 3.25 ± 0.01 for NaHMS, 3.32 ± 0.02 for NaHES, and 3.34 ± 0.04 for NH4HES at 90% RH. Their hygroscopic growth was investigated by a humidity tandem differential mobility analyzer, and hygroscopic growth factors were 1.78 ± 0.02 for NaHMS, 1.71 ± 0.02 for NaHES, and 1.68 ± 0.03 for NH4HES at 90% RH. Furthermore, the CCN activities of NaHMS, NaHES, and NH4HES were explored, and their single hygroscopicity parameters (κccn) were measured to be 0.649 ± 0.097 for NaHMS, 0.559 ± 0.069 for NaHES, and 0.434 ± 0.073 for NH4HES. In addition, the hygroscopic growth and CCN activities of binary mixtures of ammonium sulfate with one of the three hydroxyalkylsulfonates were also examined.

Abundance and fractional solubility of phosphorus and trace metals in combustion ash and desert dust: Implications for bioavailability and reactivity.

Aerosol phosphorus (P) and trace metals derived from natural processes and anthropogenic emissions have considerable impacts on ocean ecosystems, human health, and atmospheric processes. However, the abundance and fractional solubility of P and trace metals in combustion ash and desert dust, which are two of the largest emission sources of aerosols, are still not well understood. In this study, the abundance and fractional solubility of P and trace metals in seven coal fly ash samples, two municipal waste fly ash samples, and three desert dust samples were experimentally examined. It was found that the abundance of aluminum (Al) in combustion ash was comparable or even higher than that in desert dust, and, therefore, care should be taken when using Al as a tracer of desert dust. The abundance and fractional solubility of P were higher in combustion ash, with a soluble P content ~4-6 times higher than that of the desert dust, indicating that combustion ash could be an important source of bioavailable P in the atmosphere. Except for Mn, the abundance and fractional solubility of other heavy metals were higher in the combustion ash compared to the desert dust, indicating the potential importance of combustion ash in ocean ecosystems, human health, and atmospheric processes. In contrast, both the abundance and solubility of Mn were highest in the desert dust, indicating a potentially important source of soluble Mn in the atmosphere. The fractional solubilities of P and trace metals are significantly affected by acidity and ions in the extraction solutions, and it is suggested that a buffer solution can better represent the acidity of the aqueous system in the true atmospheric environment. The results of this study improve our understanding of the sources of bioavailable and reactive P and trace metals in ambient aerosols.

Water as a probe for pH measurement in individual particles using micro-Raman spectroscopy.

Atmospheric aerosol acidity impacts numerous physicochemical processes, but the determination of particle pH remains a significant challenge due to the nonconservative nature of the H+ concentration ([H+]). Traditional measurements have difficulty in describing the practical state of an aerosol because they comprise chemical components or hypotheses that change the nature of the particles. In this work, we present a direct pH measurement that uses water as a general probe to detect [H+] in individual particles by micro-Raman spectroscopy. Containing the vibrational bands of ions and water influenced by ions, the spectra of hydrated ion were decomposed from the solution spectra as standard spectra by multivariate curve resolution analysis. Meanwhile, ratios of hydrated ions were calculated between the Raman spectra and standard spectra to evaluate concentration profiles of each ion. It demonstrated that good quantitative models between the ratio and concentration for all ions including H+ can be built with correlation coefficients (R2) higher than 0.95 for the solutions. The method was further applied to individual particle pH measurement. The pH value of sulfate aerosol particles was calculated, and the standard error was 0.09 using pH values calculated from the [HSO4-]/[SO42-] as a reference. Furthermore, the applicability of the method was proven by detecting the pH value of chloride particles. Therefore, utilizing water, the most common substance, as the spectroscopic probe to measure [H+] without restriction of the ion system, this method has potential to measure the pH value of atmospheric particles with various compounds, although more work needs to be done to improve the sensitivity of the method.

A review of measurement techniques for aerosol effective density.

Density (ρ) is one of the most important physical properties of aerosol particles. Owing to the complex nature of aerosols and the challenges of measuring them, effective density (ρe) is generally used as an alternative measure. Various methods have been developed to quantify the ρe of aerosols, which provide powerful technical support and understanding of their physical properties. Here, we present a comprehensive review of the characterisation techniques of ρe currently used in the literature. Overall, six categories of measurement are identified, and the typical configuration, measurement principles, errors and field applications of each are demonstrated. Their respective advantages and disadvantages are also discussed to improve their application. Finally, we outline future directions for further technical improvement in, and instrumental development for, ρe measurement.

Heterogeneous reaction of NO2 with hematite, goethite and magnetite: Implications for nitrate formation and iron solubility enhancement.

Atmospheric processing may significantly increase solubility of iron in mineral dust, but the effects of heterogeneous reactions on iron solubility have been poorly understood. In this work, we investigated heterogeneous reaction of NO2 (15 ±â€¯1 and 2.5 ±â€¯0.1 ppmv, equal to ∼3.7 × 1014 and ∼6.2 × 1013 molecule cm-3) with hematite, magnetite and goethite at different relative humidities (RH, 0-90%), and changes in particulate nitrate and soluble iron due to heterogeneous reaction with NO2 were quantified as a function of time (up to 24 h). After reaction with 2.5 ±â€¯0.1 ppmv NO2 for 24 h (or less time), hematite and magnetite were fully saturated, while goethite was only partly deactivated. Nitrate yield was largest for goethite, and the mass ratio of formed nitrate to unreacted mineral only reached ∼1% or less after 24 h reaction. All the three minerals showed low reactivities towards NO2, and the average reactive uptake coefficients of NO2 in the first 3 h were found to be < 5 × 10-8. In addition, the increase in iron solubility was found to be small and in some cases even insignificant for the three minerals after heterogeneous reaction with NO2 for 24 h. Overall, the impacts of heterogeneous reaction of NO2 with hematite, magnetite and goethite on nitrate aerosol formation and iron solubility could be very limited.

Primary emissions and secondary organic aerosol formation from in-use diesel vehicle exhaust: Comparison between idling and cruise mode.

Diesel vehicle exhaust is an important source of carbonaceous aerosols, especially in developing countries, like China. Driving condition impacts diesel vehicle emissions, yet its influence needs further understanding especially on secondary organic aerosol (SOA) formation. In this study tailpipe exhaust from an in-use light duty diesel vehicle at idling and driving speeds of 20 and 40 km h-1 was introduced respectively into a 30 m-3 indoor smog chamber to investigate primary emissions and SOA formation during photo-oxidation. The emission factors of SO2 at 20 and 40 km h-1 were higher than those at idling, whereas the emission factors of aromatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs) and oxygenated volatile organic compounds (OVOCs) decreased when driving speeds increased. The emission factors of black carbon (BC) and primary organic aerosol (POA) at idling were comparable to those at 20 and 40 km h-1. The SOA production factors were 0.41 ±â€¯0.09 g kg-fuel-1 at idling, approximately 2.5 times as high as those at 20 km h-1 (0.16 ±â€¯0.09 g kg-fuel-1) or 40 km h-1 (0.17 ±â€¯0.09 g kg-fuel-1). Total carbonaceous aerosols, including BC, POA and SOA, from diesel vehicles at 20 and 40 km h-1 were 60-75% of those at idling, due largely to a reduction in SOA production. Measured AHs and PAHs altogether were estimated to explain <10% of SOA production, and eight major OVOCs could contribute 8.4-23% of SOA production. A preliminary comparison was further made for the same diesel vehicle at idling using diesel oils upgraded from China 3 to China 5 standard. The emission factors of total particle numbers decreased by 38% owing to less nuclei mode particles, which was probably caused by the reducing fuel sulfur content; the emission factors of BC were almost unchanged, the POA emission factors and SOA production factors however decreased by 72% and 37%.

Effects of NH3 and alkaline metals on the formation of particulate sulfate and nitrate in wintertime Beijing.

Sulfate and nitrate from secondary reactions remain as the most abundant inorganic species in atmospheric particle matter (PM). Their formation is initiated by oxidation (either in gas phase or particle phase), followed by neutralization reaction primarily by NH3, or by other alkaline species such as alkaline metal ions if available. The different roles of NH3 and metal ions in neutralizing H2SO4 or HNO3, however, are seldom investigated. Here we conducted semi-continuous measurements of SO42-, NO3-, NH4+, and their gaseous precursors, as well as alkaline metal ions (Na+, K+, Ca2+, and Mg2+) in wintertime Beijing. Analysis of aerosol acidity (estimated from a thermodynamic model) indicated that preferable sulfate formation was related to low pH conditions, while high pH conditions promote nitrate formation. Data in different mass fraction ranges of alkaline metal ions showed that in some ranges the role of NH3 was replaced by alkaline metal ions in the neutralization reaction of H2SO4 and HNO3 to form particulate SO42- and NO3-. The relationships between mass fractions of SO42- and NO3- in those ranges of different alkaline metal ion content also suggested that alkaline metal ions participate in the competing neutralization reaction of sulfate and nitrate. The implication of the current study is that in some regions the chemistry to incorporate sulfur and nitrogen into particle phase might be largely affected by desert/fugitive dust and sea salt, besides NH3. This implication is particularly relevant in coastal China and those areas with strong influence of dust storm in the North China Plain (NCP), both of which host a number of megacities with deteriorating air quality.