Decreases in Epoxide-Driven Secondary Organic Aerosol Production under Highly Acidic Conditions: The Importance of Acid-Base Equilibria.

Isoprene has the highest atmospheric emissions of any nonmethane hydrocarbon, and isoprene epoxydiols (IEPOX) are well-established oxidation products and the primary contributors forming isoprene-derived secondary organic aerosol (SOA). Highly acidic particles (pH 0-3) widespread across the lower troposphere enable acid-driven multiphase chemistry of IEPOX, such as epoxide ring-opening reactions forming methyltetrol sulfates through nucleophilic attack of sulfate (SO42-). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1). While IEPOX-SOA formation is commonly assumed to increase at low pH when more [H+] is available to protonate epoxides, we observe maximum SOA formation at pH 1 and less SOA formation at pH 0.0 and 0.4. This is attributed to limited availability of SO42- at pH values below the acid dissociation constant (pKa) of SO42- and bisulfate (HSO4-). The nucleophilicity of HSO4- is 100× lower than SO42-, decreasing SOA formation and shifting particulate products from low-volatility organosulfates to higher-volatility polyols. Current model parameterizations predicting SOA yields for IEPOX-SOA do not properly account for the SO42-/HSO4- equilibrium, leading to overpredictions of SOA formation at low pH. Accounting for this underexplored acidity-dependent behavior is critical for accurately predicting SOA concentrations and resolving SOA impacts on air quality.

Rising Alkali-to-Acid Ratios in the Atmosphere May Correspond to Increased Aerosol Acidity.

Aerosol acidity (or pH) is one central parameter in determining the health, climate, and ecological effects of aerosols. While it is traditionally assumed that the long-term aerosol pH levels are determined by the relative abundances of atmospheric alkaline to acidic substances (referred to as RC/A hereinafter), we observed contrasting pH─RC/A trends at different sites globally, i.e., rising alkali-to-acid ratios in the atmosphere may unexpectedly lead to increased aerosol acidity. Here, we examined this apparently counterintuitive phenomenon using the multiphase buffer theory. We show that the aerosol water content (AWC) set a pH "baseline" as the peak buffer pH, while the RC/A and particle-phase chemical compositions determine the deviation of pH from this baseline within the buffer ranges. Therefore, contrasting long-term pH trends may emerge when RC/A increases while the AWC or nitrate fraction decreases, or vice versa. Our results provided a theoretical framework for a quantitative understanding of the response of aerosol pH to variations in SO2, NOx versus NH3, and dust emissions, offering broad applications in studies on aerosol pH and the associated environmental and health effects.

Expiratory Aerosol pH: The Overlooked Driver of Airborne Virus Inactivation.

Respiratory viruses, including influenza virus and SARS-CoV-2, are transmitted by the airborne route. Air filtration and ventilation mechanically reduce the concentration of airborne viruses and are necessary tools for disease mitigation. However, they ignore the potential impact of the chemical environment surrounding aerosolized viruses, which determines the aerosol pH. Atmospheric aerosol gravitates toward acidic pH, and enveloped viruses are prone to inactivation at strong acidity levels. Yet, the acidity of expiratory aerosol particles and its effect on airborne virus persistence have not been examined. Here, we combine pH-dependent inactivation rates of influenza A virus (IAV) and SARS-CoV-2 with microphysical properties of respiratory fluids using a biophysical aerosol model. We find that particles exhaled into indoor air (with relative humidity ≥ 50%) become mildly acidic (pH ∼ 4), rapidly inactivating IAV within minutes, whereas SARS-CoV-2 requires days. If indoor air is enriched with nonhazardous levels of nitric acid, aerosol pH drops by up to 2 units, decreasing 99%-inactivation times for both viruses in small aerosol particles to below 30 s. Conversely, unintentional removal of volatile acids from indoor air may elevate pH and prolong airborne virus persistence. The overlooked role of aerosol acidity has profound implications for virus transmission and mitigation strategies.

Multiphase Reactions between Organic Peroxides and Sulfur Dioxide in Internally Mixed Inorganic and Organic Particles: Key Roles of Particle Phase Separation and Acidity.

Organic peroxides (POs) are ubiquitous in the atmosphere and particularly reactive toward dissolved sulfur dioxide (SO2), yet the reaction kinetics between POs and SO2, especially in complex inorganic-organic mixed particles, remain poorly constrained. Here, we report the first investigation of the multiphase reactions between SO2 and POs in monoterpene-derived secondary organic aerosol internally mixed with different inorganic salts (ammonium sulfate, ammonium bisulfate, or sodium nitrate). We find that when the particles are phase-separated, the PO-S(IV) reactivity is consistent with that measured in pure SOA and depends markedly on the water content in the organic shell. However, when the organic and inorganic phases are miscible, the PO-S(IV) reactivity varies substantially among different aerosol systems, mainly driven by their distinct acidities (not by ionic strength). The second-order PO-S(IV) rate constant decreases monotonically from 5 × 105 to 75 M-1 s-1 in the pH range of 0.1-5.6. Both proton catalysis and general acid catalysis contribute to S(IV) oxidation, with their corresponding third-order rate constants determined to be (6.4 ± 0.7) × 106 and (6.9 ± 4.6) × 104 M-2 s-1 at pH 2-6, respectively. The measured kinetics imply that the PO-S(IV) reaction in aerosol is an important sulfate formation pathway, with the reaction kinetics dominated by general acid catalysis at pH > 3 under typical continental atmospheric conditions.

Aerosol pH and Ion Activities of HSO4- and SO42- in Supersaturated Single Droplets.

Accurate determination of acidity (pH) and ion activities in aqueous droplets is a major experimental and theoretical challenge for understanding and simulating atmospheric multiphase chemistry. Here, we develop a ratiometric Raman spectroscopy method to measure the equilibrium concentration of sulfate (SO42-) and bisulfate (HSO4-) in single microdroplets levitated by aerosol optical tweezers. This approach enables determination of ion activities and pH in aqueous sodium bisulfate droplets under highly supersaturated conditions. The experimental results were compared against aerosol thermodynamic model calculations in terms of simulating aerosol ion concentrations, ion activity coefficients, and pH. We found that the Extended Aerosol Inorganics Model (E-AIM) can well reproduce the experimental results. The alternative model ISORROPIA, however, exhibits substantial deviations in SO42- and HSO4- concentrations and up to a full unit of aerosol pH under acidic conditions, mainly due to discrepancies in simulating ion activity coefficients of SO42--HSO4- equilibrium. Globally, this may cause an average deviation of ISORROPIA from E-AIM by 25 and 65% in predicting SO42- and HSO4- concentrations, respectively. Our results show that it is important to determine aerosol pH and ion activities in the investigation of sulfate formation and related aqueous phase chemistry.

Initial pH Governs Secondary Organic Aerosol Phase State and Morphology after Uptake of Isoprene Epoxydiols (IEPOX).

Aerosol acidity increases secondary organic aerosol (SOA) formed from the reactive uptake of isoprene-derived epoxydiols (IEPOX) by enhancing condensed-phase reactions within sulfate-containing submicron particles, leading to low-volatility organic products. However, the link between the initial aerosol acidity and the resulting physicochemical properties of IEPOX-derived SOA remains uncertain. Herein, we show distinct differences in the morphology, phase state, and chemical composition of individual organic-inorganic mixed particles after IEPOX uptake to ammonium sulfate particles with different initial atmospherically relevant acidities (pH = 1, 3, and 5). Physicochemical properties were characterized via atomic force microscopy coupled with photothermal infrared spectroscopy (AFM-PTIR) and Raman microspectroscopy. Compared to less acidic particles (pH 3 and 5), reactive uptake of IEPOX to the most acidic particles (pH 1) resulted in 50% more organosulfate formation, clearer phase separation (core-shell), and more irregularly shaped morphologies, suggesting that the organic phase transitioned to semisolid or solid. This study highlights that initial aerosol acidity may govern the subsequent aerosol physicochemical properties, such as viscosity and morphology, following the multiphase chemical reactions of IEPOX. These results can be used in future studies to improve model parameterizations of SOA formation from IEPOX and its properties, toward the goal of bridging predictions and atmospheric observations.

Redistribution of PM2.5 -associated nitrate and ammonium during outdoor-to-indoor transport.

Nitrate and ammonium ions are major constituents of outdoor PM2.5 . Human exposure to these ions occurs primarily indoors. To assess the adverse outcomes from exposure to them, it is necessary to quantify the relationships between outdoor and indoor PM2.5 nitrate and ammonium. The relationships for the two semi-volatile ions are more complex than those of non-volatile PM2.5 constituents (eg, sulfate, elemental carbon). This study presents a mechanistic description of their outdoor-indoor relationships that incorporates a dynamic gas-particle partitioning and key parameters such as the pH and water content of PM2.5 . Compared to measurements of nitrate and ammonium, the model has normalized mean biases of -9% and -42% and correlation coefficients of 0.95 and 0.68 for nitrate and ammonium, respectively. This suggests satisfactory agreement for nitrate, but less strong for ammonium. Sensitivity analysis on key parameters indicates that the model generally works well across a range of values typical of indoor settings. The model's performance is sensitive to pH and water content in PM2.5 , which control the gas-particle partitioning process. Indoor PM2.5 tends to be more acidic than outdoor PM2.5 , raising potential health concern. The model provides insights in exposure assessment, source apportionment, and health-composition attribution of indoor PM2.5 .

Chemical characteristics of haze particles in Xi'an during Chinese Spring Festival: Impact of fireworks burning.

Fireworks burning releases massive fine particles and gaseous pollutants, significantly deteriorating air quality during Chinese Lunar New Year (LNY) period. To investigate the impact of the fireworks burning on the atmospheric aerosol chemistry, 1-hr time resolution of PM2.5 samples in Xi'an during the winter of 2016 including the LNY were collected and detected for inorganic ions, acidity and liquid water content (LWC) of the fine aerosols. PM2.5 during the LNY was 167±87µg/m3, two times higher than the China National Ambient Air Quality Standard (75µg/m3). K+ (28wt.% of the total ion mass) was the most abundant ion in the LNY period, followed by SO42- (25wt.%) and Cl- (18wt.%). In contrast, NO3- (34wt.%) was the most abundant species in the haze periods (hourly PM2.5>75µg/m3), followed by SO42- (29.2wt.%) and NH4+ (16.3wt.%), while SO42 - (35wt.%) was the most abundant species in the clean periods (hourly PM2.5<75µg/m3), followed by NO3- (23.1wt.%) and NH4+ (11wt.%). Being different from the acidic nature in the non-LNY periods, aerosol in the LNY period presented an alkaline nature with a pH value of 7.8±1.3. LWC during the LNY period showed a robust linear correlation with K2SO4 and KCl, suggesting that aerosol hygroscopicity was dominated by inorganic salts derived from fireworks burning. Analysis of correlations between the ratios of NO3-/SO42- and NH4+/SO42- indicated that heterogeneous reaction of HNO3 with NH3 was an important formation pathway of particulate nitrate and ammonium during the LNY period.

In situ acidity and pH of size-fractionated aerosols during a recent smoke-haze episode in Southeast Asia.

The characterization of aerosol acidity has received increased attention in recent years due to its influence on atmospheric visibility, climate change and human health. Distribution of water soluble inorganic (WSI) ions in 12 different size fractions of aerosols was investigated under two different atmospheric conditions (smoke-haze and non-haze periods) in 2012 using the Micro-Orifice Uniform Deposit Impactor (MOUDI) and nano-MOUDI for the first time in Singapore. To estimate the in situ acidity ([H(+)]Ins) and in situ aerosol pH (pHIS), the Aerosol Inorganic Model version-IV under deliquescent mode of airborne particles was used at prevailing ambient temperature and relative humidity. The study revealed an increase in the levels of airborne particulate matter (PM) mass and concentrations of WSI ions for all size fractions during the smoke-haze period, which was caused by the trans-boundary transport of biomass burning-impacted air masses from Indonesia. A bimodal distribution was observed for concentrations of SO4(2-), NO3(-), Cl(-), K(+) and Na(+), whereas concentrations of NH4(+), Ca(2+) and Mg(2+) showed a single mode distribution. The concentration of WSI ions in PM1.8 during the smoke-haze period increased by 3.8 (for SO4(2-)) to 10.5 (for K(+)) times more than those observed during the non-haze period. The pHIS were observed to be lower during the smoke-haze period than that during the non-haze period for all size fractions of PM, indicating that atmospheric aerosols were more acidic due to the influence of biomass burning emissions. The particles in the accumulation mode were more acidic than those in the coarse mode.

Effects of aerosol water content and acidity on the light absorption of atmospheric humic-like substances in winter.

Atmospheric humic-like substances (HULIS) could affect regional climate due to their strong light-absorbing capacity. Daily fine particulate matter (PM2.5) samples were collected from December 18, 2016 to January 8, 2017 at an urban site in Chongqing, Southwest China. The mean concentration of HULIS in terms of carbon (HULIS-C) was 6.4 ± 3.4 µg m-3, accounting for 72% of water-soluble organic carbon. The mass absorption efficiency at 365 nm (MAE365) and absorption Ångström index (AAE) of atmospheric HULIS were 2.8 ± 0.30 m2 g-1 C and 4.6 ± 0.37, respectively. Good correlations between the light absorption coefficients of HULIS at 365 nm (Abs365) and the concentrations of K+, elemental carbon, NO3-, and NH4+ were observed, with correlation coefficients higher than 0.83, indicating that biomass burning and secondary formation were potential sources of light-absorbing HULIS, as evidenced by abundant fluorescent components related to less-oxygenated HULIS. Comparing the changes in Abs365 values, concentrations of major water-soluble inorganic ions and carbonaceous compounds in PM2.5, and environmental factors during the clean and pollution periods, we found that extensive biomass burning during the pollution period contributed significantly to the increase of Abs365 values. Moreover, the aerosol pH during the pollution period was close to 4, and NO2 concentration and aerosol water content were about 1.6 and 2.7 times higher than those during the clean period, respectively, which were favorable to form secondary HULIS through aqueous phase reactions in the presence of high NOx, resulting in an evident increase in its light absorption. Knowledge generated from this study is critical for evaluating the regional radiative forcing of brown carbon in southwest China.

Fine particulate matter from brick kilns site and roadside in Lahore, Pakistan: Insight into chemical composition, oxidative potential, and health risk assessment.

Background: Human health is seriously threatened by particulate matter (PM) pollution, which is a major environmental problem. A better indicator of biological responses to PM exposure than its mass alone is the PM "oxidative potential (OP)," or ability to oxidize target molecules. When reactive oxygen species (ROS) are generated in the OP in excess of the antioxidant capacity of body due to PM components such metals and organic species, it causes inflammation, deoxyribonucleic acid (DNA), proteins, and lipids damage. Method: The samples of fine particulate matter (PM2.5) are collected from the brick kiln site and the roadside in Lahore, Pakistan. The organic carbon (OC) and elemental carbon (EC) were estimated by carbon analyzer (DRI 2001A) using the thermal/optical transmittance (TOT) protocol. The water-soluble organic carbon (WSOC) concentration was determined using a total organic carbon analyzer (Shimadzu TOC-L CPN). Ion chromatography (Dionex ICS-900) with a conductivity detector was used to analyze the water-soluble anions (Cl-, NO3-, and SO42-) and cations (NH4+, Na+, K+, Mg2+, and Ca2+). Inductively coupled plasma-mass spectrometry (iCAP TQ ICP-MS, Thermo Scientific) was used to determine the concentrations of metals in the solution. The dithiothreitol (DTT) consumption rate was calculated using a spectrophotometer at a wavelength of 412 nm. Results: The mean concentrations of PM2.5 at the brick kiln site and roadside reported are 509.3 ± 32.3 µg/m3 and 467.5 ± 24.9 µg/m3, and the average OC/EC ratio is 1.9 ± 0.4 and 2.1 ± 0.1. primary organic carbon (POC) contributed more to OC than secondary organic carbon (SOC), which indicated the dominance of primary combustion sources. The anion equivalent (AE) to cation equivalent (CE) ratio indicated that PM2.5 is acidic at both sites due to the dominance of NO3- and SO42-. The DTT consumption rate normalized by PM2.5 mass (DTTm) and DTT consumption rate normalized by air volume (DTTv) of PM2.5 at the roadside samples are higher than at the brick kiln site due to the higher contribution of ionic species to the mass of PM2.5. Carbonaceous species of PM2.5 at both sampling sites are significantly correlated with DTTv of PM2.5, while metallic species behaved differently. The incremental lifetime cancer risk (ILCR) values (lung cancer) of As and Cr at both sampling sites, while the ILCR value of Cd at the roadside samples is exceeding the permissible limits for adults and children. The lifetime average daily dose (LADD) value for adults is higher than that for children, indicating that children are less vulnerable to metals. Conclusion: The concentration of PM2.5 at both sampling sites were exceeding the permissible limits of Pakistan' National Environmental Quality Standard (NEQS) and posing risk to the health of the local population. The POC and SOC contribution to OC at the brick kiln site and roadside in Lahore were 84.6%, 15.4% and 84.4%, 15.6%. POC at both sampling sites were the dominant carbon species indicating the dominance of primary combustion sources. The residence of Lahore poses the lung cancer risk due to Cr, As, and Cd at both sampling sites. The results of this study provide important data and evidence for further evaluation of the potential health risks of PM2.5 from brick kiln site and road side in Pakistan and formulation of efficient air-pollution control measures.

Influence of sources and atmospheric processes on metal solubility in PM2.5 in urban Guangzhou, South China.

Water-soluble metals exert a significant influence on human and ecosystem health. In this study, a comprehensive investigation was undertaken to elucidate the solubilities of metals in PM2.5 and potential influencing factors during the dry season of 2019-2020 in urban Guangzhou, South China. The observed average solubility was <20 % for Al, Fe, Sn, and Ti; 20-40 % for V, Cr, Sb, Pb, and Ni; 40-60 % for Ba and Cu; and 60-80 % for Zn, As, Se, Cd, and Mn. Metals (Al, Ti, and Fe) originated from crustal sources (e.g., soil dust) have much lower solubilities than those (Mn, Zn, As, Se, Cd, and Ba) from fossil fuel combustion sources (e.g., traffic emission, coal combustion), suggesting the dominant role the metal sources played on solubility. Enhanced solubilities of Cu, As, Se, Cd, Sn, Sb, and Pb were associated with aerosol acidity, while those of V, Cr, Mn, Ni, Zn, and Ba were linked to organic acid complexation. For the three crustal metals, the solubilities of Al and Ti primarily depended on aerosol acidity, whereas the solubility of Fe depended on both aerosol acidity under pH < 2 conditions and organic acid complexation under pH > 2 conditions. These findings underscore the primary influence of inherent properties of the metals on their solubility and reveal the varying impacts of atmospheric physicochemical processes, with changes in their solubilities being <10 % for Cd, Sn, Sb, and Pb, 10-20 % for Cu, Cr, Mn, Ni, and Ba, and 20-30 % for As, Se, and Zn.

Acidity and oxidative potential of atmospheric aerosols over a remote mangrove ecosystem during the advection of anthropogenic plumes.

To investigate the acidity and the water-soluble oxidative potential of PM10, during the continental biomass-burning plume transport, a three-year (2018-2020) winter-time campaign was conducted over a pristine island (21.35°N, 88.32°E) of Sundarban mangrove ecosystem situated at the shore of Bay of Bengal. The average PM10 concentration over Sundarban was found to be 98.3 ± 22.2 µg m-3 for the entire study period with a high fraction of non-sea-salt- SO42- and water-soluble organic carbons (WSOC) that originated from the regional solid fuel burning. The thermodynamic E-AIM(IV) model had estimated that the winter-time aerosols over Sundarban were acidic (pH:2.4 ± 0.6) and mainly governed by non-sea-salt-SO42-. The volume and mass normalized oxidative potential of PM10 was found to be 1.81 ± 0.40 nmol DTT min-1 m-3 and 18.4 ± 6.1 pmol DTT min-1 µg-1 respectively which are surprisingly higher than several urban atmospheres across the world including IGP. The acid-digested water-soluble transition metals (Cu, Mn) show higher influences in the oxidative potential (under high aerosol acidity) compared to the WSOC. The study revealed that the advection of regional solid fuel burning plume and associated non-sea-salt-SO42- is enhancing aerosol acidity and oxidative stress that in turn alters the intrinsic properties of aerosols over such marine ecosystems rich in ecology and bio-geochemistry.

Gas-particle partitioning of low-molecular-weight organic acids in suburban Shanghai: Insight into measured Henry's law constants dependent on relative humidity.

Low-molecular-weight (LMW) organic acids are among the most abundant water-soluble organic compounds, but their gas-particle partitioning mechanism remains unclear. In the present study, LMW organic acids were measured using a URG 9000D Ambient Ion Monitor in suburban Shanghai. The average concentrations of formic acid, acetic acid, oxalic acid, and methanesulfonic acid (MSA) in PM2.5 were 405 ± 116, 413 ± 11, 475 ± 266, and 161 ± 54 ng m-3, respectively. The particle fraction exceeded 30 % for formic acid and acetic acid. Model predictions underestimated the particle-phase monocarboxylic acids (MCAs) from the factor of 102 at the highest RH to 107 at the lowest RH. The average measured intrinsic Henry's law constants (Hmea) for formic acid, acetic acid, oxalic acid, and MSA were 3.8 × 107, 4.5 × 107, 8.7 × 108, and 3.4 × 107 mol L-1 atm-1, respectively, approximately four orders of magnitude higher than their literature-based intrinsic Henry's law constants (Hlit) for MCAs and approximately four orders of magnitude lower than Hlit, MSA. The ratio of Hmea /Hlit for MCAs ranged over three orders of magnitude, depending on relative humidity. The strong deviations at low RHs are attributed to the dominance of absorption by the organic phase. The discrepancy at the highest RH possibly relates to surfactant effects and dimer formation. We used Hmea as a model input for the first time to estimate the phase partitioning of particulate MCAs, finding that >80 % of MCAs resided in the organic phase under dry conditions. We propose parameterizing Hmea as model input to predict the multiphase partitioning of MCAs.

[Role of Ammonia in Aerosol Liquid Water, pH, and Secondary Inorganic Aerosols Formation at an Ammonia-rich City in Changzhou].

Ammonia （NH3） is an important alkaline reactive nitrogen, which, as a precursor of fine particulate matter, raises public health issues. In this study, online NH3, SO2, NO2, PM2.5, and its water-soluble inorganic ions were detected to deduce the influence of NH3 on aerosol liquid water content （AWC） and aerosol pH, including the formation of water-soluble secondary ions in PM2.5 in winter in Changzhou, an ammonia-rich city in the Yangtze River Delta area in winter. The results showed that NH4+ mainly existed in the form of NH4NO3 and （NH4）2SO4, and the remaining NH4+ existed as NH4Cl. Owing to the NH3-NH4+ buffer system, the aerosol pH values were found at 4.2 ± 0.4, which was positively correlated with the NH3 content. The aerosol pH value variation narrowed with the increase in PM2.5 concentration and tended to be between 4 to 5. AWC increased exponentially with the increase in humidity and SNA content, among which NH4NO3, （NH4）2SO4, and NH4Cl contributed 58.5%, 18.4%, and 8.3%, respectively, due to their hygroscopicity. Aerosol pH, AWC, and NH3-NH4+ conversion promoted the gas-to-particle conversion of SO2 and NO2. In Changzhou, rich NH3-NH4+ were found to maintain relatively high pH values, push up AWC, and promote the heterogeneous reaction of SO2, whereas NO3- generation was dominated by a homogeneous reaction, which was accelerated by NH3. According to the simulation results, relatively noticeable changes in aerosol pH and AWC could be found by the reduction of up to 30% of NH3.

Secondary inorganic aerosols and aerosol acidity at different PM2.5 pollution levels during winter haze episodes in the Sichuan Basin, China.

Wintertime fine particle (PM2.5) pollution remains to be perplexing air quality problems in many parts of China. In this study, PM2.5 compositions and aerosol acidity at different pollution levels at an urban cite in the southwest China's Sichuan Basin were investigated during a sustained winter haze episode. Organic matter was the most abundant component of PM2.5, followed by nitrate, sulfate and ammonium. Shares of organic aerosol in PM2.5 mass decreased with the elevated PM2.5 levels, while the enhancements of sulfate and secondary organic aerosol were much less than that of nitrate and ammonium during heavy pollution with increased ratios of nitrate to sulfate, implying a significant role of nitrate in the haze formation. Results also suggest the nighttime chemistry might contribute substantially to the formation of nitrate under severe pollutions. The daily average aerosol pH showed a decreasing trend with the elevated levels of PM2.5, and this increased aerosl acidity was mainly due to the fast rising secondary inorganic aerosol (SIA) concentration, with the increase in hydronium ion concentration in air (Hair+) surpassing the dilution effect of elevated aerosol liquid water content (LWC). Thermodynamic model calculations revealed that the air environment was NH3-rich with total NHx (NH3 + NH4+) greater than required NHx, and the aerosol pH exponentially declined with the decreasing excess NHx (p < 0.01). This study demonstrated that under air stagnation and NH3-rich environment during winter, the raised relative humidity (RH) would lead to an increase in LWC and thereby facilitate the aqueous chemistry processes with the neutralization capacity of NH3 to form sulfate and nitrate, which would further increase the LWC and lower the pH. This self-amplifying SIA formation might be crucial to the severe PM2.5 pollution and haze events during winter, and therefore cutting both NOx and NH3 emissions would benefit stopping the self-amplification.

Chemical characteristics and formation mechanism of secondary inorganic aerosols: The decisive role of aerosol acidity and meteorological conditions.

In recent years, there has been a growing concern about air pollution and its impact on the air quality and human health, especially for fine particulate matter (PM2.5) and its associated secondary aerosols in urban areas. This study conducted a year-long field campaign to collect PM2.5 samples day and night in an urban area of central Taiwan. Higher PM2.5 mass concentrations were observed in winter (27.7 ± 9.7 µg/m3), followed by autumn (22.5 ± 8.3 µg/m3), spring (19.2 ± 6.4 µg/m3), and summer (11.0 ± 3.1 µg/m3). The dominant formation mechanism of secondary inorganic aerosols was heterogeneous reactions of NO3- at night and homogeneous reactions of SO42- during the day. Additionally, significant correlations were observed between aerosol liquid water content (ALWC) and NO3- during nighttime, indicating the importance of aqueous-phase NO3- formation. The role of aerosol acidity was explored and a unique alkaline condition was found in spring and summer, which showed lower PM2.5 concentrations than the neutralized condition. Under the neutralized condition, higher PM2.5 concentrations were commonly found when combining the ammonium-rich regime with molar ratios of [NO3-]/[SO42-] exceeding 1.6, suggesting the importance of reducing both NH3 and NOx. Furthermore, the results showed that reducing NH3 should be prioritized under high temperature conditions, while reducing NOx became important under low temperature conditions. Clustering of backward trajectories showed that long-range transport could enhance the formation of secondary aerosols, but local emissions emerged as the main factor driving high PM2.5 concentrations. This study provides insights for policymakers to improve air quality, suggesting that different mitigation strategies should be formulated based on meteorological variables and that using clean energy for vehicles and electricity generation is important to alleviate air pollution.

Comparison of chemical composition and acidity of size-resolved inorganic aerosols at the top and foot of Mt. Hua, Northwest China: The role of the gas-particle distribution of ammonia.

Aerosol pH is not only a diagnostic indicator of secondary aerosol formation, but also a key factor in the specific chemical reaction routes that produce sulfate and nitrate. To understand the characteristics of aerosol acidity in the Mt. Hua, the chemical fractions of water-soluble inorganic ions in the atmospheric PM2.5 and size-resolved particle at the top and foot of Mt. Hua in summer 2020 were studied. The results showed the mass concentrations of PM2.5 and water-soluble ions at the foot were 2.0-2.6 times higher than those at the top. The secondary inorganic ions, i.e., SO42-, NO3-, and NH4+ (SNA) were 56 %-61 % higher by day than by night. SO42- was mainly distributed in the fine particles (Dp < 2.1 µm). NO3- showed a unimodal size distribution (peaking at 0.7-1.1 µm) at the foot and a bimodal (0.7-1.1 µm and 4.7-5.8 µm) size distribution at the top. At the top site, the distribution of NO3- in coarse particles (> 2.1 µm) was mainly attributed to the gaseous HNO3 volatilized from fine particles reacting with cations in coarse particles to form non-volatile salts (such as Ca(NO3)2). The pH values of PM2.5 were 2.7 ± 1.3 and 3.3 ± 0.42 at the top and foot, respectively. NH4+/NH3(g) plays a decisive role in stabilizing aerosol acidity. In addition, the increase of the liquid water content (LWC) at the foot facilitates the gas-particle conversion of NH3, while the H+ concentration was diluted, resulting in a decrease in acidity at the foot. NH4+/NH3 had good linear correlations with SO42-, NO3-, and LWC during the daytime at both sites, indicating that SO42-, NO3-, and LWC together affect the gas-particle distribution of ammonia by day: however, the effect of LWC at night was not evident.

Anthropogenic pollutants induce enhancement of aerosol acidity at a mountainous background atmosphere in southern China.

Aerosol acidity plays a crucial role in atmospheric physicochemical processes, climate change and human health, particularly in the formation of secondary organic aerosols (SOA). However, understanding the characteristics and driving factors of aerosol acidity in background mountains has been limited. In this study, we conducted intensive field measurements in the Nanling mountains during the dry and wet seasons to analyze aerosol pH characteristics and their driving factors using sensitivity tests. The mean aerosol pH in the background mountains was found to be 2.68 ± 0.55, with values ranging from 0.38 to 4.44, significantly lower than predicted values in northern China. Sensitivity tests revealed that aerosol acidity in the background atmosphere was more responsive to dominant chemical species (T-NH3 (= NH4+ + NH3) and SO42-) rather than relative humidity and temperature. Additionally, we observed that sulfate and ammonium, transported occasionally by dryer northern air masses, had a substantial impact on decreasing aerosol pH at the site. Similar to the southeastern United States, NH4+/NH3 also dominated the total buffer capacity of aerosol acidity in the Nanling mountains. The strong aerosol acidity in this area is expected to have adverse effects on regional air quality and climate by enhancing SOA formation and regulating the dry deposition of inorganic reactive nitrogen.

Characterization of fine particulate matter water-soluble inorganic ions and estimation of aerosol acidity at three COALESCE network sites - Mysuru, Bhopal, and Mesra - in India.

The study was carried out to understand the chemical, spatiotemporal characteristics of water-soluble inorganic ions (WSIIs), their association with PM2.5 mass, and aerosol acidity in three COALESCE (carbonaceous aerosol emissions, source apportionment, and climate impacts) network sites of India (Mesra - Eastern India, Bhopal - Central India and Mysuru - Southern India). Alternate-day 24-h integrated bulk PM2.5 samples were collected during 2019 along with on-site meteorological parameters. Annual average PM2.5 concentrations were 67 ± 46 µg m-3, 54 ± 47 µg m-3, and 30 ± 24 µg m-3 at Mesra, Bhopal, and Mysuru, respectively. PM2.5 concentrations exceeded the annual mean (40 µg m-3) recommended by the National Ambient Air Quality Standards (NAAQS) at Mesra and Bhopal. WSIIs existed in PM2.5 mass at Mesra (50.5%), Bhopal (39.6%), and Mysuru (29.2%). SO42-, NO3-, and NH4+ (SNA) were major secondary inorganic ions in total WSIIs, with an annual average of 88.4% in Mesra and 82.0% in Bhopal 78.4% in Mysuru. Low NO3-/SO42- ratios annually at Mesra (0.41), Bhopal (0.44), and Mysuru (0.24) indicated that stationary sources dominated vehicular emissions (1.0). Aerosol acidity varied from region to region and season to season depending on the presence of NH4+, the dominant counter-ion to neutralize anions. Aerosols were near-neutral or alkaline at all three sites, except during the pre-monsoon season in Mysuru. An assessment of neutralization pathways for major anions [SO42- + NO3-] suggests that they mainly existed as sulfate and nitrate salts such as ammonium sulfate ((NH4)2SO4) and ammonium bisulfate (NH4HSO4) in conjunction with ammonium nitrate (NH4NO3).