Aerosol pH Research Articles

Direct quantification of changes in pH within single levitated microdroplets and the kinetics of nitrate and chloride depletion.

The hygroscopicity and pH of aqueous microdroplets and smaller aerosols control their impacts on human health and the climate. Nitrate depletion and chloride depletion through the partitioning of HNO3 and HCl into the gas phase are processes that are enhanced in micron-sized and smaller aqueous droplets and this depletion influences both hygroscopicity and pH. Despite a number of studies, uncertainties remain about these processes. While acid evaporation and the loss of HCl or HNO3 have been observed during dehydration, there is a question as to the rate of acid evaporation and whether this can occur in fully hydrated droplets at higher relative humidity (RH). To directly elucidate the kinetics of nitrate and chloride depletion through evaporation of HNO3 and HCl, respectively at high RH, single levitated microdroplets are probed with cavity-enhanced Raman spectroscopy. Using glycine as a novel in situ pH probe, we are able to simultaneously measure changes in microdroplet composition and pH over timescales of hours. We find that the loss of chloride from the microdroplet is faster than that of nitrate, and the calculated rate constants infer that depletion is limited by the formation of HCl or HNO3 at the air-water interface and subsequent partitioning into the gas phase.

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.

Impacts of the COVID-19 lockdown on atmospheric oxidizing capacity and secondary aerosol formation over the Beijing-Tianjin-Hebei region in Winter-Spring 2020

By using WRF-Chem coupled with a heterogeneous reaction mechanism for sulfate formation, this study investigated the impact of meteorological condition and emission changes on chemical species, atmospheric oxidizing capacity (AOC), and secondary aerosol formation during the COVID-19 lockdown period from 23 January to April 8, 2020, focusing on a severe haze event on 7–14 February. The model with the new sulfate formation scheme reasonably reproduces the spatial-temporal distribution of meteorological variables and chemical species, and significantly improves predictions for both sulfate and SO2 concentrations, as well as for PM2.5, ammonium, and nitrate to some extent. It is found that the adverse meteorological conditions were the main cause for the haze event formation, whereas emission reduction due to the lockdown somewhat decreased PM2.5 concentration on average in the Beijing-Tianjin-Hebei (BTH) region. Compared with the same period in 2019, increased surface air temperature and relative humidity (RH) and decreased planetary boundary layer height (PBLH) facilitated accumulation of pollutants and formation of secondary aerosols during the haze episode in 2020, whereas the emission reduction due to the lockdown led to decreases in SO2, NO2, primary PM2.5 (PPM2.5), black carbon (BC), primary organic aerosols (POA), nitrate and ammonium concentrations, but increases in O3, sulfate and secondary organic aerosol (SOA) concentrations, due to the combined effect of changes in emissions and AOC. Gas and aqueous phase oxidation of SO2 accounted for approximately 24% of sulfate formation, while the heterogeneous reaction of Mn-catalytic oxidation of SO2 on aerosol surfaces dominated sulfate formation (76%) during the haze episode in the BTH region. Both adverse meteorological conditions and emission reductions increased heterogeneous sulfate formation rate mainly through altering aerosol surface area (ASA), pH, and Mn2+ concentration. Chemical species varied diversely during the three subperiods before (Period-1, 15–22 January) and during the lockdown (Period-2, 23 January to 5 March and Period-3, 6 March to 8 April) over the BTH. NO2 concentration firstly decreased and then rebounded, whereas O3 concentration increased gradually from the Period-1 to Period-3. All aerosols except SOA decreased throughout the lockdown period, whereas SOA peaked in the Period-2 due to its strong sensitivity to increasing AOC. Sulfate concentration decreased from the Period-1 to Period-2, mainly due to more adverse meteorological conditions in the Period-1, although sulfate increased slightly due to increasing AOC in the Period-2. The large difference in the direction and magnitude of species variations during the COVID-19 lockdown indicates the complex interplay among meteorology, emission, and chemistry.

Dust emission reduction enhanced gas-to-particle conversion of ammonia in the North China Plain

Ammonium salt is an important component of particulate matter with aerodynamic diameter less than 2.5 µm (PM2.5) and has significant impacts on air quality, climate, and natural ecosystems. However, a fundamental understanding of the conversion kinetics from ammonia to ammonium in unique environments of high aerosol loading is lacking. Here, we report the uptake coefficient of ammonia (γNH3) on ambient PM2.5 varying from 2.2 × 10−4 to 6.0 × 10−4 in the North China Plain. It is significantly lower than those on the model particles under simple conditions reported in the literature. The probability-weighted γNH3 increases obviously, which is well explained by the annual decrease in aerosol pH due to the significant decline in alkali and alkali earth metal contents from the emission source of dust. Our results elaborate on the complex interactions between primary emissions and the secondary formation of aerosols and the important role of dust in atmospheric chemistry.

Long-term trends and drivers of aerosol pH in eastern China

Abstract. Aerosol acidity plays a key role in regulating the chemistry and toxicity of atmospheric aerosol particles. The trend of aerosol pH and its drivers is crucial in understanding the multiphase formation pathways of aerosols. Here, we reported the first trend analysis of aerosol pH from 2011 to 2019 in eastern China, calculated with the ISORROPIA model based on observed gas and aerosol compositions. The implementation of the Air Pollution Prevention and Control Action Plan led to −35.8 %, −37.6 %, −9.6 %, −81.0 % and 1.2 % changes of PM2.5, SO42-, NHx, non-volatile cations (NVCs) and NO3- in the Yangtze River Delta (YRD) region during this period. Different from the drastic changes of aerosol compositions due to the implementation of the Air Pollution Prevention and Control Action Plan, aerosol pH showed a minor change of −0.24 over the 9 years. Besides the multiphase buffer effect, the opposite effects from the changes of SO42- and non-volatile cations played key roles in determining this minor pH trend, contributing to a change of +0.38 and −0.35, respectively. Seasonal variations in aerosol pH were mainly driven by the temperature, while the diurnal variations were driven by both temperature and relative humidity. In the future, SO2, NOx and NH3 emissions are expected to be further reduced by 86.9 %, 74.9 % and 41.7 % in 2050 according to the best health effect pollution control scenario (SSP1-26-BHE). The corresponding aerosol pH in eastern China is estimated to increase by ∼0.19, resulting in 0.04 less NO3- and 0.12 less NH4+ partitioning ratios, which suggests that NH3 and NOx emission controls are effective in mitigating haze pollution in eastern China.

Unexpected/contrary behavior of aerosol mass concentration in response to the individual components’ concentration reduction in Kitakyushu, Japan

In the suburbs of Kitakyushu, Japan, the inorganic aerosol mass concentration (IAM) was about 32.7 µg/m3, with the aerosol pH of 3.3. To study the thermodynamics of aerosol when its individual components’ concentration is reduced, sensitive tests were performed using the ISORROPIA II model, in which the seven control species—TNaCl, TNH4+, TSO42−, TNO3−, TMg2+, TK+, and TCa2+—were taken into account. IAM and inorganic aerosol pH after reducing TNaCl, TNO3−, TMg2+, TK+, and TCa2+ responded linearly (0% ≤ concentration reduction ratio (CRR) ≤ 100%, with the exception of 100% in TNaCl); the nonlinear variations of these two parameters could be observed by controlling TNH4+ and TSO42−. Unexpected aerosol behavior occurred at 100% reduction of TNaCl, which was caused by the sudden increase of NO3−, NH4+, and aerosol liquid water content (ALWC); the increase of IAM was also observed after controlling TSO42− (60% ≤ CRR ≤ 100%) and TCa2+ (0% ≤ CRR ≤ 100%), which was mainly related to the variation of ALWC driven by the response of CaSO4. Multiple regression analysis showed that ALWC was statistically and strongly related to the variations of NO3−, Cl−, SO42−, HSO4−, HNO3, and NH3 (P < 0.05), with regression coefficients of 1.68, 5.23, 1.83, 2.81, 0.34, and 0.57, respectively. The highest coefficient (5.23) was found for Cl−, revealing that sea salts significantly influenced particle responses. Overall, this study comprehensively investigated aerosol characteristics and inner responses for the reduction of components, which is of great significance for a better understanding of atmospheric chemistry in Kitakyushu, Japan.

Quantitative Decomposition of Influencing Factors to Aerosol pH Variation over the Coasts of the South China Sea, East China Sea, and Bohai Sea

Quantitative Decomposition of Influencing Factors to Aerosol pH Variation over the Coasts of the South China Sea, East China Sea, and Bohai Sea

A study on wildfire impacts on greenhouse gas emissions and regional air quality in South of Orléans, France

Wildfire events are increasing globally which may be partly associated with climate change, resulting in significant adverse impacts on local, regional air quality and global climate. In September 2020, a small wildfire (burned area: 36.3 ha) event occurred in Souesmes (Loir-et-Cher, Sologne, France), and its plume spread out over 200 km on the following day as observed by the MODIS satellite. Based on measurements at a suburban site (∼ 50 km northwest of the fire location) in Orléans and backward trajectory analysis, young wildfire plumes were characterized. Significant increases in gaseous pollutants (CO, CH4, N2O, VOCs, etc.) and particles (including black carbon) were found within the wildfire plumes, leading to a reduced air quality. Emission factors, defined as EF (X) = ∆X/∆CO (where, X represents the target species), of various trace gases and black carbon within the young wildfire plumes were determined accordingly and compared with previous studies. Changes in the ambient ions (such as ammonium, sulfate, nitrate, chloride, and nitrite in the particle- and gas- phase) and aerosol properties (e.g., aerosol water content, aerosol pH) were also quantified and discussed. Moreover, we estimated the total carbon and climate-related species (e.g., CO2, CH4, N2O, and BC) emissions and compared them with fire emission inventories. Current biomass burning emission inventories have uncertainties in estimating small fire burned areas and emissions. For instance, we found that the Global Fire Assimilation System (GFAS) may underestimate emissions (e.g., CO) of this small wildfire while other inventories (GFED and FINN) showed significant overestimation. Considering that it is the first time to record wildfire plumes in this region, related atmospheric implications are presented and discussed.

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.

Secondary inorganic aerosol chemistry and its impact on atmospheric visibility over an ammonia-rich urban area in Central Taiwan

This study investigated the hourly inorganic aerosol chemistry and its impact on atmospheric visibility over an urban area in Central Taiwan, by relying on measurements of aerosol light extinction, inorganic gases, and PM2.5 water-soluble ions (WSIs), and simulations from a thermodynamic equilibrium model. On average, the sulfate (SO42−), nitrate (NO3−), and ammonium (NH4+) components (SNA) contributed ∼90% of WSI concentrations, which in turn made up about 50% of the PM2.5 mass. During the entire observation period, PM2.5 and SNA concentrations, aerosol pH, aerosol liquid water content (ALWC), and sulfur and nitrogen conversion ratios all increased with decreasing visibility. In particular, the NO3− contribution to PM2.5 increased, whereas the SO42− contribution decreased, with decreasing visibility. The diurnal variations of the above parameters indicate that the interaction and likely mutual promotion between NO3− and ALWC enhanced the hygroscopicity and aqueous-phase reactions conducive for NO3− formation, thus led to severely impaired visibility. The high relative humidity (RH) at the study area (average 70.7%) was a necessary but not sole factor leading to enhanced NO3− formation, which was more directly associated with elevated ALWC and aerosol pH. Simulations from the thermodynamic model depict that the inorganic aerosol system in the study area was characterized by fully neutralized SO42− (i.e. a saturated factor in visibility reduction) and excess NH4+ amidst a NH3-rich environment. As a result, PM2.5 composition was most sensitive to gas-phase HNO3, and hence NOx, and relatively insensitive to NH3. Consequently, a reduction of NOx would result in instantaneous cuts of NO3−, PM2.5, and ALWC, and hence improved visibility. On the other hand, a substantial amount of NH3 reduction (>70%) would be required to lower the aerosol pH, driving more than 50% of the particulate phase NO3− to the gas phase, thereby making NH3 a limiting factor in shifting PM2.5 composition.

The role of source emissions in sulfate formation pathways based on chemical thermodynamics and kinetics model

Sulfate is a major PM2.5 constituent and poses a significant threat to ecosystems and human health, which has attracted lots of attention to the sulfate formation mechanism. In recent years, there has been great scientific interest in the multiphase oxidation of SO2 in aqueous aerosol particles. Many factors are involved in the reaction process, including precursor SO2, oxidants/catalysts, and aerosol acidity, which are three channels closely related to the source emission. The conjoint analysis of source emissions and sulfate aqueous formation can provide a scientific basis for designing effective strategies, though the related research is extremely limited. Here, we applied an improved solute strength-dependent chemical Thermodynamics & Kinetics model (for aqueous pathway contribution) and the Partial Target Transformation-Positive matrix factor model (for source apportionment) to explore the role of source emission in sulfate aqueous formation. The results indicated H2O2 aqueous oxidation was the dominant pathway (65.9 %), and secondary nitrate source may grow together with sulfate formation from H2O2 pathway. H2O2 and TMI pathways were related to higher SOR (sulfur oxidation rate). TMI pathway was significant in summer (54.6 %) and increased with secondary sources and vehicle exhaust. NO2 pathway was more significant at low secondary source and high coal combustion (higher contribution of NO2 pathway appeared in winter, 24.7 %). While high formation rate of the O3 pathway always occurred at low source levels. Coal combustion and vehicle exhaust showed obvious effects on sulfate aqueous formation. Notably, aerosol acidity is a significant factor related to sources and plays a key role in sulfate formation. The result also suggested aerosol pH may be more important than the amounts of substances involved in the oxidation reaction. The findings in this work can provide useful information for better understanding sulfate aqueous formation and offer a scientific basis for designing strategies for air pollution control and sulfate mitigation.

Simulations of aerosol pH in China using WRF-Chem (v4.0): sensitivities of aerosol pH and its temporal variations during haze episodes

Abstract. Aerosol pH is a fundamental property of aerosols in terms of atmospheric chemistry and its impact on air quality, climate, and health. Precise estimation of aerosol pH in chemical transport models (CTMs) is critical for aerosol modeling and thus influences policy development that partially relies on results from model simulations. We report the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) simulated PM2.5 pH over China during a period with heavy haze episodes in Beijing, and explore the sensitivity of the modeled aerosol pH to factors including emissions of nonvolatile cations (NVCs) and NH3, aerosol phase state assumption, and heterogeneous production of sulfate. We find that default WRF-Chem could predict spatial patterns of PM2.5 pH over China similar to other CTMs, but with generally lower pH values, largely due to the underestimation of alkaline species (NVCs and NH3) and the difference in thermodynamic treatments between different models. Increasing NH3 emissions in the model would improve the modeled pH in comparison with offline thermodynamic model calculations of pH constrained by observations. In addition, we find that the aerosol phase state assumption and heterogeneous sulfate production are important in aerosol pH predictions for regions with low relative humidity (RH) and high anthropogenic SO2 emissions, respectively. These factors should be better constrained in model simulations of aerosol pH in the future. Analysis of the modeled temporal trend of PM2.5 pH in Beijing over a haze episode reveals a clear decrease in pH from 5.2 ± 0.9 in a clean period to 3.6 ± 0.5 in a heavily polluted period. The increased acidity under more polluted conditions is largely due to the formation and accumulation of secondary species including sulfuric acid and nitric acid, even though being modified by alkaline species (NVCs, NH3). Our result suggests that NO2 oxidation is unlikely to be important for heterogeneous sulfate production during the Beijing haze as the effective pH for NO2 oxidation of S(IV) is at a higher pH of ∼ 6.

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in wintertime aerosols of Northwest China

Dicarboxylic acids are one of the important water-soluble organic compounds in atmospheric aerosols, causing adverse effects to both climate and human health. More attention has therefore been paid to organic acids in aerosols. In this study, the molecular distribution and diurnal variations of wintertime dicarboxylic acids in a rural site of Guanzhong Plain, Northwest China, were explored. Oxalic acid (C2, day: 438.9 ± 346.8 ng m−3, night: 398.8 ± 392.3 ng m−3) is the most abundant compound followed by methylglyoxal (mGly, day: 207.8 ± 281.1 ng m−3, night: 222.9 ± 231.0 ng m−3) and azelaic (C9, day: 212.8 ± 269.1 ng m−3, night: 211.4 ± 136.7 ng m−3) acid. The ratios of C9/C6 and C9/Ph indicating that atmospheric dicarboxylic acids in winter in the region mainly come from biomass burning. Furthermore, secondary inorganic ions (NO3−, SO42−, and NH4+), relative humidity, liquid water content, and in-situ pH of aerosols are highly linearly correlated with C2, suggesting that liquid phase oxidation is an important pathway for the formation of dicarboxylic acids. The δ13C analysis of C2 suggested that lighter carbon isotope compositions tend to be oxidized to form aqueous-phase secondary organic aerosols (aqSOA), leading to the decay of 13C in aqSOA products rather than aerosol aging. This study provides a theoretical basis for the mechanism of formation of dicarboxylic acid.

Seasonal variations in aerosol acidity and its driving factors in the eastern Indo-Gangetic Plain: A quantitative analysis

This study employs ISORROPIA-II for the evaluation of aerosol acidity and quantification of contributions from chemical species and meteorological parameters to acidity variation in the Indian context. PM2.5 samples collected during summer (April–July 2018), post-monsoon (September–November 2018), and winter (December 2018–January 2019) from a rural receptor location in the eastern Indo-Gangetic Plain (IGP) were analyzed for ionic species, water-soluble organic carbon (WSOC), and organic and elemental carbon (OC, EC) fractions. This was followed by estimation of the in situ aerosol pH and liquid water content (LWC) using the forward mode of ISORROPIA-II, which is less sensitive to measurement uncertainty compared to the reverse mode, for a K+-Ca2+-Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O system. Aerosol pH was moderately acidic (summer: 2.93 ± 0.67; post-monsoon: 2.67 ± 0.23; winter: 3.15 ± 0.34) and was most sensitive to SO42− and total ammonium (TNH3) variation. The LWC of aerosol showed an increasing trend from summer (16.6 ± 13.6 μg m−3) through winter (32.9 ± 10.4 μg m−3). With summer as the baseline, the largest changes in aerosol pH during the other seasons was driven by SO42− (ΔpH: −0.70 to −0.82 units), followed by TNH3 (ΔpH: +0.25 to +0.38 units) with K+ and temperature being significant only during winter (ΔpH: +0.51 and + 0.46 units, respectively). The prevalent acidity regime provided three major insights: i) positive summertime Cl− depletion (49 ± 20%) as a consequence of SO42− substitution increased aerosol pH by 0.03 ± 0.20 units and decreased LWC by 2.4 ± 5.9 μg m−3; ii) the rate of strong acidity (H+str) neutralization and the [H+str]/[SO42−] molar ratio suggested the existence of bounded acidity in ammonium-rich (winter) conditions; and iii) significant correlations between LWC, WSOC, and secondary organics during post-monsoon and winter pointed towards a possible indirect role of WSOC in enhancing LWC of aerosol, thereby increasing pH. Given the inability of proxies such as H+str and charge ratios to accurately represent aerosol pH as demonstrated here, this study emphasizes the need for rigorous thermodynamic model-based evaluation of aerosol acidity in the Indian scenario.

Seasonal Aerosol Acidity, Liquid Water Content and Their Impact on Fine Urban Aerosol in SE Canada

This study explores the drivers of aerosol pH and their impact on the inorganic fraction and mass of aerosol in the S.E. Canadian urban environments of Hamilton and Toronto, Ontario. We find that inter-seasonal pH variability is mostly driven by temperature changes, which cause variations of up to one pH unit. Wintertime acidity is reduced, compared to summertime values. Because of this, the response of aerosol to precursors fundamentally changes between seasons, with a strong sensitivity of aerosol mass to levels of HNO3 in the wintertime. Liquid water content (LWC) fundamentally influences the aerosol sensitivity to NH3 and HNO3 levels. In the summertime, organic aerosol is mostly responsible for the LWC at Toronto, and ammonium sulfate for Hamilton; in the winter, LWC was mostly associated with ammonium nitrate at both sites. The combination of pH and LWC in the two sites also affects N dry deposition flux; NO3− fluxes were comparable between the two sites, but NH3 deposition flux at Toronto is almost twice what was seen in Hamilton; from November to March N deposition flux slows down leading to an accumulation of N as NO3− in the particle phase and an increase in PM2.5 levels. Given the higher aerosol pH in Toronto, aerosol masses at this site are more sensitive to the emission of HNO3 precursors compared to Hamilton. For both sites, NOx emissions should be better regulated to improve air quality during winter; this is specifically important for the Toronto site as it is thermodynamically more sensitive to the emissions of HNO3 precursors.

Direct Measurement of pH Evolution in Aerosol Microdroplets Undergoing Ammonium Depletion: A Surface-Enhanced Raman Spectroscopy Approach.

Accurately measuring the pH of atmospheric aerosols is a prerequisite for understanding the multiphase chemistry that profoundly affects the environment and climate systems. Despite the advancements of experimental techniques for in situ pH measurements in aerosols, current studies are limited to measuring the static pH of aerosol microdroplets with an unperturbed composition. This steady-state scenario, however, deviates from the real-world aerosols undergoing atmospheric aging reactions, specifically, those characterized with a spontaneous displacement of strong bases (or acids) with high volatility. Here, we introduce a continuous and in situ measurement of aerosol pH by using a 4-mercaptopyridine-functionalized silver nanoparticle probe and surface-enhanced Raman spectroscopy. We find that the ammonium depletion─a spontaneous displacement of ammonium by dicarboxylic acid salts─continuously acidifies aerosol water over time. The decaying trends of pH in the aerosols under various humidity conditions can be unified with a universal exponential function. Such an exponentially decaying function further indicates that the ammonium depletion reaction is a self-limiting process. Our technique can be applied to study the dynamic change of aerosol acidity during the complex atmospheric aging processes, toward elucidating their implications on atmospheric chloride, nitrate, and ammonium cycles.

Acidity of Size-Resolved Sea-Salt Aerosol in a Coastal Urban Area: Comparison of Existing and New Approaches

Aging of sea-salt aerosol and the corresponding phase partitioning behavior of HCl/Cl– were monitored and studied in the Halifax Fog and Air Quality Study (HaliFAQS) field campaign in Canada in the early summer of 2019. Ionic chemical composition of ambient aerosol from total suspended particles (TSPs) to 10 nm was sampled and measured into 14 size ranges, which showed that aerosol at the sampling location was mainly composed of sea-salt constituents with little influence from anthropogenic emissions of secondary inorganic precursors. The size-resolved pH of aged sea-salt aerosol was calculated by Extended Aerosol Inorganic Model (E-AIM) IV and a newly derived method based on the measurement of NH3/NH4+ and HNO3/NO3– or HCl/Cl– coupled phase partitioning behavior. The latter pH calculation method does not require information about the aerosol liquid water content or complete water-soluble ion measurement, compensating for the role of oxidized organics to influence the proton activity. In comparison, E-AIM calculation requires the input of all major hygroscopic species. The size-resolved pH calculated by E-AIM IV generally agrees with the one calculated by NH3–HCl coupled phase partitioning. The sensitivities of HCl and HNO3 phase partitioning to aerosol pH are studied with both observational data and conceptual modeling, which gives evidence that the phase partitioning of HCl is more sensitive and therefore more reflective of aerosol pH changes than HNO3 in sea-salt dominated atmospheres where particles typically have pH > 3. The higher concentration and more reliable measurement also make HCl a more suitable choice to track pH changes in this study.

Modeling of reducing NH4NO3 in PM2.5 under high ammonia emission in urban areas: Based on high-resolution data

At present, the air quality in urban areas in China has continued to improve, but PM2.5 is still severely polluted in autumn and winter and is difficult to meet the Chinese standard. With the renovation of coal-fired boilers and the transformation of ultra-low emissions in factories, NO3− has gradually become the main inducing species for high levels of PM2.5. In this study, a high-resolution (1 h) online instrument was used to analyze the characteristics of atmospheric PM2.5 in the autumn and winter periods from October 2019 to February 2020 at Zhengzhou University in Zhengzhou. The inorganic nitrate in PM2.5 mainly existed in the form of semivolatile NH4NO3, and the method of reducing NH4NO3 was studied through data analysis. The basic method of reducing particulate nitrate in PM2.5 is not only to reduce nitrate precursors (NOx) but also to transform particulate nitrate into gas by reducing the aerosol pH value (enhancing aerosol acidity). The simulation analysis of NHx (NHx = NH3+NH4+), NO3T (NO3T=HNO3+NO3−), and SO42− reduction using the thermodynamic model ISORROPIA-II revealed that total ammonia (TA) has an obvious peak clipping effect on particulate NO3− when it is reduced by 60% and can effectively reduce NH4NO3 in PM2.5. The reliability and credibility of the data results were enhanced through long-term observation and local time analysis, and reducing TA and NO3− in areas with high ammonia emissions was proven to be feasible. This study is beneficial for formulating measures to reduce the average annual concentration of PM2.5 in ammonia-rich areas.

Atmospheric Processing at the Sea‐Land Interface Over the South China Sea: Secondary Aerosol Formation, Aerosol Acidity, and Role of Sea Salts

AbstractSea salts act as an important medium for atmospheric processing. One intensive field campaign in the September–October period of 2019 was conducted at a subtropical coastal site over the South China Sea. Unexpected high concentrations of acidic gaseous precursors were observed, yielding high sulfate in PM2.5. Na+ ranked as the third highest inorganic species, about half of NH4+. Significant cation deficiency was found due to the ammonia‐poor environment. Diel patterns of most air pollutants from land breeze were stronger than that from marine breeze and presented pronounced unimodal distributions, which were ascribed to complex chemical processing mixed with regional transport. Thermodynamic equilibrium model (ISORROPIA II) simulation revealed sea salts could be internally mixed with fine particle secondary species and suggested evident multiphase reactions on sea salts. The simulated aerosol pH reached as low as 1.63 ± 0.50, which was related to high sulfate, insufficient alkaline species, and low aerosol liquid water content. During a continuous sea breeze episode, SO42− was underpredicted by 2.89 ± 3.85 μg m−3 if Na+ was not considered in ISORROPIA simulation. The retrieved Na+ ‐related ion pairs (NaCl, NaHSO4, and Na2SO4) accounted for about one‐fourth of the total inorganic aerosols. This study highlighted that intense atmospheric processing on sea salts occurred in fine particles and the mixing state between sea salts and other aerosol species should be considered in aerosol acidity prediction and secondary aerosol formation in coastal regions.

Significant coal combustion contribution to water-soluble brown carbon during winter in Xingtai, China: Optical properties and sources

To understand the characteristics of atmospheric brown carbon (BrC), daily PM2.5 samples in Xingtai, a small city in North China Plain (NCP), during the four seasons of 2018-2019, were collected and analyzed for optical properties and chemical compositions. The light absorption at 365 nm (absλ=365 nm) displayed a strong seasonal variation with the highest value in winter (29.0±14.3 M/m), which was 3.2∼5.4-fold of that in other seasons. A strong correlation of absλ=365 nm with benzo(b)fluoranthene (BbF) was only observed in winter, indicating that coal combustion was the major source for BrC in the season due to the enhanced domestic heating. The mass absorbing efficiency of BrC also exhibited a similar seasonal pattern, and was found to correlate linearly with the aerosol pH, suggesting a positive effect of aerosol acidity on the optical properties and formation of BrC in the city. Positive matrix factorization (PMF) analysis further showed that on a yearly basis the major source for BrC was biomass burning, which accounted for 34% of the total BrC, followed by secondary formation (26.7%), coal combustion (21.3%) and fugitive dust (18%). However, the contribution from coal combustion was remarkably enhanced in winter, accounting for ∼40% of the total. Our work revealed that more efforts of “shifting coal to clean energy” are necessary in rural areas and small cities in NCP in order to further mitigate PM2.5 pollution in China.