Aerosol Liquid Water Research Articles

Source apportionment of soot particles and aqueous-phase processing of black carbon coatings in an urban environment

Abstract. The impacts of soot particles on climate and human health depend on the concentration of black carbon (BC) as well as the thickness and composition of the coating material, i.e., organic and inorganic compounds internally mixed with BC. In this study, the size-resolved chemical composition of BC-containing aerosol was measured using a high-resolution soot particle aerosol mass spectrometer (SP-AMS) during wintertime in Fresno, California, a location influenced by abundant combustion emissions and frequent fog events. Concurrently, particle optical properties were measured to investigate the BC absorption enhancement. Positive matrix factorization (PMF) analysis was performed on the SP-AMS mass spectral measurements to explore the sources of soot particles and the atmospheric processes affecting the properties of BC coatings. The analysis revealed that residential woodburning and traffic are the dominant sources of soot particles. Alongside primary soot particles originating from biomass burning (BBOABC) and vehicles (HOABC) two distinct types of processed BC-containing aerosol were identified: fog-related oxidized organic aerosol (FOOABC) and winter-background OOABC (WOOABC). Both types of OOABC showed evidence of having undergone aqueous processing, albeit with differences. The concentration of FOOABC was substantially elevated during fog events, indicating the formation of aqueous secondary organic aerosol (aqSOA) within fog droplets. On the other hand, WOOABC was present at a relatively consistent concentration throughout the winter and was likely related to the formation of secondary organic aerosol (SOA) in both the gas phase and aerosol liquid water. By comparing the chemical properties and temporal variations in FOOABC and WOOABC, we gain insights into the key aging processes of BC aerosol. It was found that aqueous-phase reactions facilitated by fog droplets had a significant impact on the thickness and chemical composition of BC coatings, thereby affecting the light absorption and hygroscopic properties of soot particles. These findings underscore the important role of chemical reactions occurring within clouds and fogs and influencing the climate forcing of BC aerosol in the atmosphere.

Impact of ozonation on the formation of particulate nitrosodi-methylamine (NDMA) in atmosphere

The contribution of ozonation to the formation of particulate nitrosodi-methylamine (NDMA) in the aqueous aerosol phase was investigated using measurement data from 2018 in Seoul, Republic of Korea and a box model. The correlation between the NDMA concentration and aerosol liquid water content and box model results showed that aqueous aerosol phase reactions, including nitrosation and ozonation, might contribute to the formation of NDMA. The concentration of NDMA and the ratio of O3/dimethylamine exhibited a negative correlation, suggesting that the contribution of ozonation to NDMA formation may not be significant. Furthermore, when the daily concentration of NDMA exceeded 10 ng/m3, the pH was 3.96 ± 0.48, indicating that the impact of ozonation on NDMA concentration might not be significant. To quantitatively investigate the contribution of ozonation, the ozonation mechanism that forms NDMA was included in the box model developed in our previous study. The model results showed that the ozonation contributed to the ambient concentration of NDMA (7.9 ± 3.8% (winter); 1.9 ± 3.0% (spring); 10.0 ± 0.77% (summer); 3.6 ± 7.3% (autumn)). It is estimated that the relatively higher O3/NOx ratio in summer (1.63 ± 0.69; 0.64 ± 0.52 (winter); 1.14 ± 0.92 (spring); 0.52 ± 0.54 (autumn)) could enhance ozonation and that relatively lower pH in summer (2.2 ± 0.4; 5.3 ± 1.2 (winter); 3.9 ± 1.2 (spring); 3.9 ± 0.7 (autumn)) could hinder nitrosation compared to that in other seasons.

Predicting Atmospheric Water-Soluble Organic Mass Reversibly Partitioned to Aerosol Liquid Water in the Eastern United States.

Water-soluble organic matter (WSOM) formed through aqueous processes contributes substantially to total atmospheric aerosol, however, the impact of water evaporation on particle concentrations is highly uncertain. Herein, we present a novel approach to predict the amount of evaporated organic mass induced by sample drying using multivariate polynomial regression and random forest (RF) machine learning models. The impact of particle drying on fine WSOM was monitored during three consecutive summers in Baltimore, MD (2015, 2016, and 2017). The amount of evaporated organic mass was dependent on relative humidity (RH), WSOM concentrations, isoprene concentrations, and NOx/isoprene ratios. Different models corresponding to each class were fitted (trained and tested) to data from the summers of 2015 and 2016 while model validation was performed using summer 2017 data. Using the coefficient of determination (R2) and the root-mean-square error (RMSE), it was concluded that an RF model with 100 decision trees had the best performance (R2 of 0.81) and the lowest normalized mean error (NME < 1%) leading to low model uncertainties. The relative feature importance for the RF model was calculated to be 0.55, 0.2, 0.15, and 0.1 for WSOM concentrations, RH levels, isoprene concentrations, and NOx/isoprene ratios, respectively. The machine learning model was thus used to predict summertime concentrations of evaporated organics in Yorkville, Georgia, and Centerville, Alabama in 2016 and 2013, respectively. Results presented herein have implications for measurements that rely on sample drying using a machine learning approach for the analysis and interpretation of atmospheric data sets to elucidate their complex behavior.

Aqueous-Phase Reactions of Anthropogenic Emissions Lead to the High Chemodiversity of Atmospheric Nitrogen-Containing Compounds during the Haze Event.

Nitrogen-containing organic compounds (NOCs), a type of important reactive-nitrogen species, are abundant in organic aerosols in haze events observed in Northern China. However, due to the complex nature of NOCs, the sources, formation, and influencing factors are still ambiguous. Here, the molecular composition of organic matters (OMs) in hourly PM2.5 samples collected during a haze event in Northern China was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We found that CHON compounds (formulas containing C, H, O, and N atoms) dominated the OM fractions during the haze and showed high chemodiversity and transformability. Relying on the newly developed revised-workflow and oxidation-hydrolyzation knowledge for CHON compounds, 64% of the major aromatic CHON compounds (>80%) could be derived from the oxidization or hydrolyzation processes. Results from FT-ICR MS data analysis further showed that the aerosol liquid water (ALW)-involved aqueous-phase reactions are important for the molecular distribution of aromatic-CHON compounds besides the coal combustion, and the ALW-involved aromatic-CHON compound formation during daytime and nighttime was different. Our results improve the understanding of molecular composition, sources, and potential formation of CHON compounds, which can help to advance the understanding for the formation, evolution, and control of haze.

Key Factors Determining the Formation of Sulfate Aerosols Through Multiphase Chemistry—A Kinetic Modeling Study Based on Beijing Conditions

AbstractSevere haze in Beijing is characterized by the rapid formation of sulfate via the multiphase oxidation of SO2. While many factors, including aerosol oxidants and atmospheric variables, were discovered and investigated, their relative importance remains unclear. Herein, based on the field observation data obtained in Beijing, China, we developed a kinetic model to explore the key factors that determine the multiphase formation of sulfate. Sensitivity tests give the kinetics of each oxidation pathway varying with pH and temperature, based on which the total sulfate formation rate at room temperature (298 K) is calculated to be generally greater than that at standard temperature (273 K), especially during nighttime. Interfacial oxidants are responsible for sulfate formation within a wide pH range, and transition metal ions become more efficient with increased temperature. The multiphase chemistry is additionally affected by aerosol liquid water content (ALWC), particle radius (Rp), and ionic strength (IS). Within the usual aerosol acidity, the kinetic discrepancy induced by different ALWC levels is more significant at the lower temperature, in contrast to the temperature dependence related to Rp, and the effect of IS depends highly on pH. Machine learning reveals the potential importance of temperature, acidity, and Rp. Temperature and acidity are impactful for the formation of both aqueous and interfacial sulfates, whereas Rp only affects the interfacial processes. The discrepancy between nighttime and daytime is considered throughout this study. Overall, this study reveals the key factors for multiphase sulfate formation and is recommended for kinetic evaluation in future laboratory research.

Significant Reductions in Secondary Aerosols after the Three-Year Action Plan in Beijing Summer.

Air quality in China has continuously improved during the Three-Year Action Plan (2018-2020); however, the changes in aerosol composition, properties, and sources in Beijing summer remain poorly understood. Here, we conducted real-time measurements of aerosol composition in five summers from 2018 to 2022 along with WRF-Community Multiscale Air Quality simulations to characterize the changes in aerosol chemistry and the roles of meteorology and emission reductions. Largely different from winter, secondary inorganic aerosol and photochemical-related secondary organic aerosol (SOA) showed significant decreases by 55-67% in summer, and the most decreases occurred in 2021. Comparatively, the decreases in the primary aerosol species and gaseous precursors were comparably small. While decreased atmospheric oxidation capacity as indicated by ozone changes played an important role in changing SOA composition, the large decrease in aerosol liquid water and small increase in particle acidity were critical for nitrate changes by decreasing gas-particle partitioning substantially (∼28%). Analysis of meteorological influences demonstrated clear and similar transitions in aerosol composition and formation mechanisms at a relative humidity of 50-60% in five summers. Model simulations revealed that emission controls played the decisive role in reducing sulfate, primary OA, and anthropogenic SOA during the Three-Year Action Plan, while meteorology affected more nitrate and biogenic SOA.

Size‐Dependent Nighttime Formation of Particulate Secondary Organic Nitrates in Urban Air

AbstractParticulate secondary organic nitrates play a key role in understanding secondary organic aerosol production, ozone formation, and the atmospheric nitrogen cycle. However, the formation of particulate secondary organic nitrates in ambient air remains poorly understood. In this study, the nighttime formation processes of particulate secondary organic nitrates were investigated based on size‐resolved aerosols measured in urban air of China with a soot particle long‐time‐of‐flight aerosol mass spectrometer. The results show a bimodal size distribution of particulate secondary organic nitrates, peaking at ∼350 nm in condensation mode (100–400 nm) and ∼750 nm in droplet mode (400–2,500 nm), respectively. The nighttime formation processes of particulate secondary organic nitrates in the two size modes were respectively governed by temperature‐dependent condensation and aqueous‐phase processing. In particular, the mass concentration of particulate secondary organic nitrates in condensation mode was positively correlated with nitrate radical production and negatively correlated with temperature, suggesting that the formation processes were associated with the gas‐particle conversion of nitrate radical oxidation products. In contrast, the enhanced particulate secondary organic nitrates in droplet mode were predominantly contributed by aqueous‐phase processing, as indicated by the strong positive correlation with aerosol liquid water content and typical fragment ions from aqueous processing products (r = 0.52–0.59, P &lt; 0.01). Our results highlight the potential of a size‐dependent mechanism to elucidate the formation processes of particulate secondary organic nitrates.

High-time-resolution chemical composition and source apportionment of PM2.5 in northern Chinese cities: implications for policy

Abstract. Fine particulate matter (PM2.5) pollution is still one of China's most important environmental issues, especially in northern cities during wintertime. In this study, intensive real-time measurement campaigns were conducted in Xi'an, Shijiazhuang, and Beijing to investigate the chemical characteristics and source contributions of PM2.5 and explore the formation of heavy pollution for policy implications. The chemical compositions of PM2.5 in the three cities were all dominated by organic aerosol (OA) and nitrate (NO3-). Results of source apportionment analyzed by a hybrid environmental receptor model (HERM) showed that the secondary formation source contributed more to PM2.5 compared to other primary sources. Biomass burning was the dominant primary source in the three pilot cities. The contribution of coal combustion to PM2.5 is non-negligible in Xi'an and Shijiazhuang but is no longer an important contributor in the capital city of Beijing due to the execution of a strict coal-banning policy. The potential formation mechanisms of secondary aerosol in the three cities were further explored by establishing the correlations between the secondary formation sources and aerosol liquid water content (ALWC) and Ox (O3+NO2), respectively. The results showed that photochemical oxidation and aqueous-phase reaction were two important pathways of secondary aerosol formation. According to source variations, air pollution events that occurred in campaigns were classified into three types: biomass-combustion-dominated, secondary-formation-source-dominated, and a combination of primary and secondary sources. Additionally, this study compares the changes in chemical composition and source contributions of PM2.5 in past decades. The results suggest that the clean-energy replacements for rural households should be urgently encouraged to reduce the primary source emissions in northern China, and collaborative control on ozone and particulate matter needs to be continuously promoted to weaken the atmosphere oxidation capacity for the sake of reducing secondary aerosol formation.

Thermodynamical framework for effective mitigation of high aerosol loading in the Indo-Gangetic Plain during winter

The Indo-Gangetic Plain (IGP) experiences severe air pollution every winter, with ammonium chloride and ammonium nitrate as the major inorganic fractions of fine aerosols. Many past attempts to tackle air pollution in the IGP were inadequate, as they targeted a subset of the primary pollutants in an environment where the majority of the particulate matter burden is secondary in nature. Here, we provide new mechanistic insight into aerosol mitigation by integrating the ISORROPIA-II thermodynamical model with high-resolution simultaneous measurements of precursor gases and aerosols. A mathematical framework is explored to investigate the complex interaction between hydrochloric acid (HCl), nitrogen oxides (NOx), ammonia (NH3), and aerosol liquid water content (ALWC). Aerosol acidity (pH) and ALWC emerge as governing factors that modulate the gas-to-particle phase partitioning and mass loading of fine aerosols. Six "sensitivity regimes" were defined, where PM1 and PM2.5 fall in the "HCl and HNO3 sensitive regime", emphasizing that HCl and HNO3 reductions would be the most effective pathway for aerosol mitigation in the IGP, which is ammonia-rich during winter. This study provides evidence that precursor abatement for aerosol mitigation should not be based on their descending mass concentrations but instead on their sensitivity to high aerosol loading.

Assessment of submicron aerosol liquid water content and mass-based growth factors in South Asian outflow over the Indian Ocean

Aerosol-bound water, a ubiquitous and abundant component of atmospheric aerosols, has an impact on regional climate, visibility, human health, the hydrological cycle, and atmospheric chemistry. Yet, the intricate relationship between aerosol liquid water (ALWC) and chemical composition and relative humidity (RH) was not well understood. The present study explores ALWC derived from the ISORROPIA II model using real-time, high-resolution data of non-refractory submicron chemical species and meteorological parameters (temperature and RH) collected over the Indian Ocean as part of the ICARB (Integrated Campaign for Aerosols, Gases, and Radiation Budget)-2018 experiment. Results show that ALWC values over the South Eastern Arabian Sea (SEAS) were found to be higher by 4–6 times than those observed over the Equatorial Indian Ocean (EIO) due to a large decrease in aerosol loading from SEAS to EIO. ALWC peaked in the early morning hours (4:00–7:00), with greater values during the nighttime and lower values during the daytime across SEAS, which is comparable with RH variation. While the ratio of organics-to-SO42− mass fraction linearly decreased with increasing mass-based growth factors (MGFs) over EIO, such a scenario was not observed over SEAS. The latitudinal gradient of mass fraction of ALWC had shown a decrease towards EIO, consistent with organic fraction. The extinction coefficient of the dry mass of submicron particles is noticeably increased by 40 % by ALWC over SEAS and EIO. Moreover, ALWC could enhance the aerosol negative forcing by an average of 66 % (64 %) over SEAS (EIO) at the top of the atmosphere during the cruise period. These inferences imply that ALWC is the key factor in assessing the role of aerosols on atmospheric radiative forcing. Overall, the present study highlights the serious need to consider the ALWC in climate forcing simulations, particularly in moist tropical environments where their effect can be significant.

Characteristics and atmospheric processes of water-soluble ions in PM2.5 and PM10 over an industrial city in the National Capital Region (NCR) of India

This study investigates water-soluble inorganic ions (WSIIs), their potential formation mechanism, particle bound water content and acidity (pH) in ambient aerosols in Ghaziabad, an industrial city located downwind of Delhi, the Indian National Capital. 24-hour integrated PM2.5 and PM10 samples were collected using collocated samplers at two receptor locations every third day throughout the year. The samples were collected on Nylon filter substrates (preceded by a denuder upstream for capturing acidic gases) and Teflon filter substrates for WSII and mass measurements, respectively. Further, on-site meteorological parameters were recorded at both locations. The annual average PM concentrations observed were: PM2.5: 144 ± 81 μgm−3 (Site A), 163 ± 95 μgm−3 (Site B); and PM10: 245 ± 116 μgm−3 (Site A), 279 ± 152 μgm−3 (Site B). On average, SO42−, NO3−, Cl− and NH4+ contributed to ∼90% to PM2.5WSII mass and ∼82% to PM10WSII mass, which in turn made up ∼35% of PM2.5 mass and ∼23% of the PM10 mass across both sites. SO42− concentration was found to be highest followed by NO3−, NH4+ and Cl− for both PM fractions. Mann-Whitney U test revealed that both sites were similar with respect to WSII mass indicating city's airshed average concentration with respect to the major ions. The highest WSII contribution to the total PM was found in winter season (37–40% for PM2.5 and 27–31% for PM10) followed by monsoon (36–38% for PM2.5 and 18–21% for PM10), post-monsoon (28–34% for PM2.5 and 21–23% for PM10) and pre-monsoon (21–27% for PM2.5 and 15% for PM10). High contribution during winter was because of higher emissions of precursor gases in combination with moderate relative humidity (36–59%) and minimal precipitation (average ∼0.2 mm). Sulphur Oxidation Ratio and Nitrogen Oxidation Ratio indicated high photochemical oxidation with a greater extent of SO42− formation compared to NO3−. Although high concentrations of NH3 gas were observed, there was insufficient NH4+ ions for neutralizing counter ions with Ammonium Neutralization Ratio values of 0.76±0.14 for PM2.5 and 0.62±0.14 for PM10. Finally, aerosol liquid water content (ALWC) and acidity were estimated using a thermodynamic equilibrium model, ISORROPIA-II. It was found that PM2.5 pH varied from 2.9 to 6.2 (avg. 4.4±0.8) and the PM2.5 mass doubled at RH ∼90% because of the high particle bound water. Consequently, a reduction in SO2 would result in instantaneous cuts of SO42−, PM2.5, and ALWC.

Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles

Abstract. Aerosol liquid water (ALW) is a unique reaction medium, but its chemistry is poorly understood. For example, little is known of photooxidant concentrations – including hydroxyl radicals (⚫OH), singlet molecular oxygen (1O2*), and oxidizing triplet excited states of organic matter (3C*) – even though they likely drive much of ALW chemistry. Due to the very limited water content of particles, it is difficult to quantify oxidant concentrations in ALW directly. To predict these values, we measured photooxidant concentrations in illuminated aqueous particle extracts as a function of dilution and used the resulting oxidant kinetics to extrapolate to ALW conditions. We prepared dilution series from two sets of particles collected in Davis, California: one from winter (WIN) and one from summer (SUM). Both periods are influenced by biomass burning, with dissolved organic carbon (DOC) in the extracts ranging from 10 to 495 mg C L−1. In the winter sample, the ⚫OH concentration is independent of particle mass concentration, with an average value of 5.0 (± 2.2) × 10−15 M, while in summer ⚫OH increases with DOC in the range (0.4–7.7) × 10−15 M. In both winter and summer samples, 3C* concentrations increase rapidly with particle mass concentrations in the extracts and then plateau under more concentrated conditions, with a range of (0.2–7) × 10−13 M. WIN and SUM have the same range of 1O2* concentrations, (0.2–8.5) × 10−12 M, but in WIN the 1O2* concentration increases linearly with DOC, while in SUM 1O2* approaches a plateau. We next extrapolated the relationships of oxidant formation rates and sinks as a function of particle mass concentration from our dilute extracts to the much more concentrated condition of aerosol liquid water. Predicted ⚫OH concentrations in ALW (including mass transport of ⚫OH from the gas phase) are (5–8) × 10−15 M, similar to those in fog/cloud waters. In contrast, predicted concentrations of 3C* and 1O2* in ALW are approximately 10 to 100 times higher than in cloud/fogs, with values of (4–9) × 10−13 M and (1–5) × 10−12 M, respectively. Although ⚫OH is often considered the main sink for organic compounds in the atmospheric aqueous phase, the much higher concentrations of 3C* and 1O2* in aerosol liquid water suggest these photooxidants will be more important sinks for many organics in particle water.

Secondary Formation of Atmospheric Brown Carbon in China Haze: Implication for an Enhancing Role of Ammonia.

Optical characteristics and molecular compositions of brown carbon (BrC) were investigated during winter 2019 at a rural site of China with a focus on nitro-aromatic compounds (NACs) and imidazoles (IMs). The abundance of gaseous nitrophenols relative to CO during the campaign maximized at noontime, being similar to O3, while the particulate NACs during the haze periods strongly correlated with toluene and NO2, suggesting that NACs in the region are largely formed from the gas-phase photooxidation. Strong correlations of particulate IMs in the dry haze periods with the mass ratio of EC/PM2.5 and the concentration of levoglucosan were observed, indicating that IMs during the dry events are largely derived from biomass burning emissions. However, an increase in IMs with the increasing aerosol liquid water content and pH was observed in the humid haze events, along with much lower abundances of levoglucosan and K+ relative to PM2.5, suggesting that IMs were mostly formed from aqueous reactions in the humid haze periods. These IMs exponentially increased with an increasing NH3 owing to an aqueous reaction of carbonyls with free ammonia. Our findings for the first time revealed an enhancing effect of ammonia on BrC formation in China, especially in humid haze periods.

Mist cannon trucks can exacerbate the formation of water-soluble organic aerosol and PM2.5 pollution in the road environment

Abstract. Mist cannon trucks have been widely applied in megacities in China to reduce the road dust, since they are considered to be more water saving and efficient than the traditional sprinkling trucks. However, their effect on the formation of water-soluble organic compounds and the pollution control of fine particles (PM2.5) remains unknown. We characterized the variations of chemical compositions in PM2.5 collected on the road sides during the simulated operations of mist cannon truck and traditional sprinkling truck via Fourier transform ion cyclotron resonance mass spectrometry and ion chromatography. The mass concentrations of water-soluble organic carbon in PM2.5 showed a significant increase (62 %–70 %) after air spraying. Furthermore, we found that water-soluble organic compounds, particularly organic nitrates, increased significantly via the interactions of reactive gas-phase organics, atmospheric oxidants and aerosol liquid water after air spraying, although the air spraying had a better effect on suppressing road dust than the ground aspersion. Moreover, the formation of PM2.5 on the road segment where the mist cannon truck passed by was promoted, with an increase of up to 13 % in mass concentration after 25–35 min, on average. Thus, the application of mist cannon trucks potentially worsens the road atmospheric environment through the increase in PM2.5 levels and the production of a large number of water-soluble organic compounds in PM2.5. The overall results provide not only valuable insights to the formation processes of water-soluble organic compounds associated with aerosol liquid water in the road environment but also management strategies to regulate the operation of mist cannon trucks in China.

Formation pathways of organic aerosols over a tropical coastal atmosphere

The characteristics of non-refractory submicron aerosols (NR-PM1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O3+NO2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (кorganics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere.

Impact of HO2 aerosol uptake on radical levels and O3 production during summertime in Beijing

Abstract. The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing &lt;0.3 % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. &lt;0.1 ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

Organosulfur compounds in ambient fine particulate matter in an urban region: Findings of a nontargeted approach

Organosulfur compounds (OSCs) are important components of fine particulate matter (PM2.5); however, little information is available on OSCs in urban regions due to their chemical complexity, especially for novel species such as aromatic sulfonates. To supplement the detection technique and systematically identify OSCs, in this study we developed a nontargeted approach based on gas chromatography and high-resolution mass spectrometry (GC-HRMS) to screen OSCs in PM2.5 of urban Beijing and provide field evidence for their source and formation mechanism. 76 OSCs were found through mass difference of sulfur isotopes and characteristic sulfur-containing fragments. 6 species were confirmed as aromatic sulfonates by authentic standards. 32 OSCs showed higher levels in the heating season, presumably because of the intensive emission, especially from coal combustion. While certain species, with 2-sulfobenzoic acid as the representative, were 2.6-times higher in the non-heating season than in the heating season. Such species were significantly correlated with ozone and aerosol liquid water content (r = 0.2–0.8, p < 0.05), implying an oxidation-involved aqueous-phase formation in the atmosphere. In addition, with an average proportion of ∼95 % of the total sulfobenzoic acids, the predominance of the 2-substitution product over its isomers of 3- or 4-sulfobenzoic acid suggests a more plausible mechanism of radical-initiated reaction of phthalic acid followed by sulfonation, with atmospheric reactivity indicated by ozone and temperature as the determining factor. This study provided not only a nontargeted approach for OSCs in ambient PM2.5, but also field evidence on their secondary formation proposed in previous simulation studies.

Aerosol liquid water in PM2.5 and its roles in secondary aerosol formation at a regional site of Yangtze River Delta

Aerosol liquid water content (ALWC) plays an important role in secondary aerosol formation. In this study, a whole year field campaign was conducted at Shanxi in north Zhejiang Province during 2021. ALWC estimated by ISORROPIA-II was then investigated to explore its characteristics and relationship with secondary aerosols. ALWC exhibited a highest value in spring (66.38 µg/m3), followed by winter (45.08 µg/m3), summer (41.64 µg/m3), and autumn (35.01 µg/m3), respectively. It was supposed that the secondary inorganic aerosols (SIA) were facilitated under higher ALWC conditions (RH > 80%), while the secondary organic species tended to form under lower ALWC levels. Higher RH (> 80%) promoted the NO3– formation via gas-particle partitioning, while SO42– was generated at a relative lower RH (> 50%). The ALWC was more sensitive to NO3– (R = 0.94) than SO42– (R = 0.90). Thus, the self-amplifying processes between the ALWC and SIA enhanced the particle mass growth. The sensitivity of ALWC and OX (NO2 + O3) to secondary organic carbon (SOC) varied in different seasons at Shanxi, more sensitive to aqueous-phase reactions (daytime R = 0.84; nighttime R = 0.54) than photochemical oxidation (daytime R = 0.23; nighttime R = 0.41) in wintertime with a high level of OX (daytime: 130–140 µg/m3; nighttime: 100–140 µg/m3). The self-amplifying process of ALWC and SIA and the aqueous-phase formation of SOC will enhance aerosol formation, contributing to air pollution and reduction of visibility.

Online chemical characterization of atmospheric fine secondary aerosols and organic nitrates in summer Nanjing, China

The mechanisms leading to secondary aerosol pollution in the Yangtze Delta region (such as Nanjing) are still poorly constrained. Here we conducted a field campaign to elucidate the chemical characteristics of fine aerosols, with a focus on variations and formation mechanisms of secondary components in summer Nanjing. The average PM1 mass concentration was 18.88 μg m−3 and was dominated by the secondary species (78%). Secondary inorganic species accounted for 30% of PM1 mass and high PM1 loading was closely relevant with nitrate rather than sulfate. Nitrate was mainly produced from nighttime heterogeneous/aqueous process (production rate of 0.38 g/g H2O) and its variation was driven by thermodynamic equilibrium. On the other hand, sulfate was governed by daytime photochemical production (production rate of 0.013 g/g Ox)(Ox=NO2 + O3) while contribution of aqueous process was minor. Positive matrix factorization identified and quantified a traffic-related hydrocarbon OA (HOA), a cooking OA (COA), and four SOA factors including a local secondary OA (LSOA), a less oxygenated OA (LO-OOA), a moderately oxygenated OA (MD-OOA), and a more-oxidized oxygenated OA (MO-OOA). LSOA was likely from local photochemical conversion of HOA and COA; LO-OOA was semi-volatile thus evaporation/diffusion would offset its weak photochemical production. MO-OOA was very clearly linked with photochemistry, based on its afternoon enhancement and tight positive correlations with Ox (0.029 g/g Ox, occupying ∼60% of photochemical SOA production) and sulfate. MD-OOA was a minor contributor of SOA (∼6%) but it was clearly from aqueous process given the strong positive correlation with aerosol liquid water content (ALWC) and nitrate. Both nitrate and MD-OOA concentrations increased against pH while those of sulfate and MO-OOA decreased. We further investigated the organic nitrate (ON) characteristics, and found that ON was a very minor component of OA in summer Nanjing (0.08–0.14 μg m−3, 0.6–1.1% of OA) and it was predominantly associated with aqueous process. Overall, this work reveals in details formation processes of different secondary species, and therefore is insightful for future air pollution modelling and efficient control in similar regions.

Evaluation of Probes to Measure Oxidizing Organic Triplet Excited States in Aerosol Liquid Water.

Oxidizing triplet excited states of organic matter (3C*) drive numerous reactions in fog/cloud drops and aerosol liquid water (ALW). Quantifying oxidizing triplet concentrations in ALW is difficult because 3C* probe loss can be inhibited by the high levels of dissolved organic matter (DOM) and copper in particle water, leading to an underestimate of triplet concentrations. In addition, illuminated ALW contains high concentrations of singlet molecular oxygen (1O2*), which can interfere with 3C* probes. Our overarching goal is to find a triplet probe that has low inhibition by DOM and Cu(II) and low sensitivity to 1O2*. To this end, we tested 12 potential probes from a variety of compound classes. Some probes are strongly inhibited by DOM, while others react rapidly with 1O2*. One of the probe candidates, (phenylthiol)acetic acid (PTA), seems well suited for ALW conditions, with mild inhibition and fast rate constants with triplets, but it also has weaknesses, including a pH-dependent reactivity. We evaluated the performance of both PTA and syringol (SYR) as triplet probes in aqueous extracts of particulate matter. While PTA is less sensitive to inhibition than SYR, it results in lower triplet concentrations, possibly because it is less reactive with weakly oxidizing triplets.